Sulfonium salt, photo-acid generator, and photosensitive resin composition

ABSTRACT

There is provided a sulfonium salt having high photosensitivity to the i-line. The invention relates to a sulfonium salt represented by formula (1) described below: [in formula (1), R 1  to R 6  each independently represent an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly) alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, m 1  to m 6  each represent the number of occurrences of each of R 1  to R 6 , m 1 , m 4 , and m 6  each represent an integer of 0 to 5, m 2 , m 3 , and m 5  each represent an integer of 0 to 4, and X −  represents a monovalent polyatomic anion].

TECHNICAL FIELD

The invention relates firstly to a sulfonium salt and secondly to a photo-acid generator, more specifically, a photo-acid generator containing a specific sulfonium salt suitable for curing a cationically polymerizable compound by the action of an active energy ray such as light, an electron beam, or an X-ray. The invention relates thirdly to a curable composition containing the photo-acid generator and a cured product obtained by curing the composition. The invention relates fourthly to a chemically amplified positive photoresist composition containing the photo-acid generator and a method for forming a resist pattern using the composition. The invention relates fifthly to a chemically amplified negative photoresist composition containing the photo-acid generator.

BACKGROUND ART

Photo-fabrication, which is currently in vogue for a precision microfabrication technique, is the generic name for techniques in which various precision parts such as semiconductor packages are manufactured by applying a photosensitive resin composition to the surface of a material to be processed to form a coating film, patterning the coating film by photolithographic techniques, and performing electroforming, which generally involves chemical etching, electrolytic etching, and/or electroplating, using the patterned coating film as a mask.

Known conventional photo-acid generators for use in curing cationically polymerizable compounds such as epoxy compounds by the action of active energy rays such as light, electron beams, or X-rays include triarylsulfonium salts (Patent Document 1), phenacylsulfonium salts having a naphthalene skeleton (Patent Document 2), dialkylbenzylsulfonium salts (Patent Document 3), and sulfonium salts having an introduced thioxanthone skeleton (Patent Document 4).

At present, the i-line with a wavelength of 365 nm is widely used as exposure light in photolithographic processes using photoresists. Some reasons for this are that medium- or high-pressure mercury lamps, which are available as irradiation light sources at a low cost and have high emission intensity, can be used, and LED lamps having an emission wavelength in the i-line region (360 nm to 390 nm) are currently becoming widespread. It is therefore considered that a need for photo-acid generators having high sensitivity to the i-line will further increase in the future.

However, some existing photo-acid generators such as triarylsulfonium salts (Patent Document 1), phenacylsulfonium salts having a naphthalene skeleton (Patent Document 2), and dialkylbenzylsulfonium salts (Patent Document 3) have low sensitivity to the i-line and therefore need to be used in combination with a sensitizer so that the sensitivity can be increased. Sulfonium salts having an introduced thioxanthone skeleton (Patent Document 4) also have a problem that their i-line absorbance is too high so that light may fail to reach a deep portion at the time of curing a thick film, which causes curing failure.

Moreover, in recent years, as the size of electronic devices has further decreased, high-density packaging of semiconductor packages has progressed, in which the packaging density has been increased based on multi-pin thin film packaging or package downsizing, or two- or three-dimensional packaging techniques using flip-chip method. Connection terminals formed by such high-density packaging techniques include projecting electrodes (mounted terminals) such as bumps projecting on packages; and metal posts for connecting mounted terminals to rewiring parts extending from peripheral terminals on a wafer, which are placed with high precision on a substrate.

Materials for use in such high-precision photo-fabrication include positive photosensitive resin compositions containing a naphthoquinonediazide group-containing compound (see Patent Document 5). However, such materials have a problem that they have low sensitivity to the i-line (365 nm), which is an exposure light source generally used in photolithographic processes.

A chemically amplified positive resist composition in which an oxime sulfonate compound is used as an acid generator is proposed as a photosensitive resin composition for reducing the above problem (see Patent Document 6). When this composition is irradiated with (exposed to) radiations, an acid is generated from the photo-acid generator, and heat treatment after the exposure facilitates the diffusion of the acid and the acid-catalyzed reaction, so that the base resin in the resin composition undergoes a change in solubility in an alkali. Such a composition is called a positive photoresist, because the base resin, which is insoluble in alkali before the exposure, is made alkali-soluble. However, this resist composition has low storage stability and therefore needs complicated storage-temperature control and has a practical problem.

There are also known chemically amplified positive resist compositions in which a triarylsulfonium salt compound is used as a photo-acid generator (Non-Patent Documents 1 and 2 and Patent Documents 7 and 8). Although they have high storage stability, they are not considered to have sufficient sensitivity to the i-line.

Conventionally, polyimide-based resins, which are excellent in heat resistance, mechanical properties, and the like, have been widely used to form surface protecting films, interlayer dielectric films, and others for use in semiconductor devices in electronics.

There are also proposed various photosensitive polyimide-based resins having photosensitivity for an improvement in the precision of film formation by high integration of semiconductor devices (Patent Documents 9, 10, and 11).

Such compositions need a cyclization process in which heat treatment is performed at high temperature for imidization, and therefore, film loss may occur after curing, or process conditions such as temperature control conditions are complicated.

To reduce such problems, there are also proposed photosensitive resin compositions produced with an alkali-soluble resin having a phenolic hydroxyl group (Patent Documents 12 and 13).

Such compositions are negative photoresist compositions, in which an acid is generated from a photo-acid generator by exposure to light and facilitates the reaction between a crosslinking agent and a base resin so that the resin becomes insoluble in a developing solution. However, such compositions contain a triazine-type photo-acid generator and therefore have a problem that the acid generated from the triazine-based photo-acid generator is hydrochloric or hydrobromic acid, which is volatile and pollutes facilities.

Conventional sulfonium salt-based photo-acid generators also have a problem that they have low sensitivity to the i-line (365 nm) which is an exposure light source generally used in photolithographic processes.

PRIOR ART DOCUMENTS Patent Documents

-   Patent Document 1: Japanese Patent Application Laid-Open (JP-A) No.     50-151997 -   Patent Document 2: JP-A No. 09-118663 -   Patent Document 3: JP-A No. 02-178303 -   Patent Document 4: JP-A No. 08-165290 -   Patent Document 5: JP-A No. 2002-258479 -   Patent Document 6: JP-A No. 2000-66385 -   Patent Document 7: JP-A No. 2003-231673 -   Patent Document 8: JP-A No. 2002-193925 -   Patent Document 9: JP-A No. 54-145794 -   Patent Document 10: JP-A No. 03-186847 -   Patent Document 11: JP-A No. 08-50354 -   Patent Document 12: JP-A No. 2008-77057 -   Patent Document 13: WO2008-117619

Non-Patent Documents

-   Non-Patent Document 1: M. J. O'Brien, J. V. Crivello, SPIE -   Vol. 920, Advances in Resist Technology and Processing, p. 42 (1988) -   Non-Patent Document 2: H. ITO, SPIE Vol. 920, Advances in Resist     Technology and Processing, p. 33 (1988)

SUMMARY OF THE INVENTION Problems to be Solved by the Invention

Under the above circumstances, a first object of the invention is to provide a new sulfonium salt having high photosensitivity to the i-line.

A second object of the invention is to provide a new acid generator that comprises a sulfonium salt and has high photosensitivity to the i-line and high compatibility with a cationically polymerizable compound such as an epoxy compound, and also has excellent storage stability when formulated with a cationically polymerizable compound such as an epoxy compound.

A third object of the invention is to provide an energy ray-curable composition and a cured product each produced with the above acid generator.

A fourth object of the invention is to provide a chemically amplified positive photoresist composition, which has good storage stability and is capable of forming a resist having high sensitivity to the i-line, and a method for forming a resist pattern.

A fifth object of the invention is to provide a chemically amplified negative photoresist composition, which has good storage stability and is capable of forming a resist having high sensitivity to the i-line, and a method for forming a resist pattern.

Means for Solving the Problems

The inventors have found that a sulfonium salt represented by formula (1) described below is suitable for achieving the above objects. Thus, the invention provides a sulfonium salt represented by formula (1):

[In formula (1), R¹ to R⁶ each independently represent an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly) alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, m¹ to m⁶ each represent the number of occurrences of each of R¹ to R⁶, m¹, m⁴, and m⁶ each represent an integer of 0 to 5, m², m³, and m⁵ each represent an integer of 0 to 4, and X⁻ represents a monovalent polyatomic anion].

The invention also provides a photo-acid generator comprising the above sulfonium salt.

The invention also provides an energy ray-curable composition comprising the above photo-acid generator and a cationically polymerizable compound.

The invention further provides a cured product obtained by curing the above energy ray-curable composition.

The invention further provides a chemically amplified positive photoresist composition comprising the above photo-acid generator and a resin ingredient (B) increasing its solubility in an alkali under the action of an acid.

The invention further provides a method for forming a resist pattern, comprising: a lamination step of laminating a photoresist layer with a thickness of 5 to 150 μm comprising any one of the above chemically amplified positive photoresist compositions to obtain a photoresist laminate; an exposure step of site-selectively irradiating the photoresist laminate with light or a radiation; and a development step of developing the photoresist laminate after the exposure step to obtain a resist pattern.

The invention further provides a chemically amplified negative photoresist composition comprising: the above photo-acid generator; an ingredient (F) that is an alkali-soluble resin having a phenolic hydroxyl group; and a crosslinking agent ingredient (G).

The invention further provides any one of the above chemically amplified negative photoresist compositions, further comprising a crosslinked fine particles ingredient (H).

The invention further provides a cured product obtained by curing any one of the above chemically amplified negative photoresist compositions.

Effects of the Invention

The sulfonium salt of the invention has excellent photosensitivity to active energy rays such as visible light, ultraviolet rays, electron beams, and X-rays, and high compatibility with a cationically polymerizable compound such as an epoxy compound, and also has excellent storage stability when formulated with a cationically polymerizable compound such as an epoxy compound.

The photo-acid generator of the invention has excellent curing properties under the action of ultraviolet light, particularly, i-line, when used to cure a cationically polymerizable compound, and makes it possible to cure a cationically polymerizable compound with no sensitizer. The photo-acid generator of the invention also has excellent thick-film-curing properties.

The energy ray-curable composition of the invention contains the above photo-acid generator and therefore can be cured with ultraviolet light. The energy ray-curable composition of the invention also has high storage stability and excellent cost effectiveness and workability, because no sensitizer needs to be used.

The cured product of the invention can be obtained with no sensitizer and therefore is free from the problem of discoloration or deterioration, which would be caused by any residual sensitizer.

The chemically amplified positive photoresist composition and the chemically amplified negative photoresist composition of the invention each contain the above photo-acid generator and therefore can form a resist with high sensitivity to the i-line. The chemically amplified positive photoresist composition and the chemically amplified negative photoresist composition of the invention also have high storage stability and can form a good resist pattern shape.

MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the invention are described in detail.

In formula (1), examples of the alkyl group for R¹ to R⁶ include straight chain alkyl groups having 1 to 18 carbon atoms (such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, and n-octadecyl), branched chain alkyl groups having 1 to 18 carbon atoms (such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, and isooctadecyl), and cycloalkyl groups having 3 to 18 carbon atoms (such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and 4-decylcyclohexyl).

In formula (1), examples of the alkoxy group for R¹ to R⁶ include straight or branched chain alkoxy groups having 1 to 18 carbon atoms (such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, decyloxy, dodecyloxy, and octadecyloxy).

In formula (1), examples of the alkylcarbonyl group for R¹ to R⁶ include straight or branched chain alkylcarbonyl groups having 2 to 18 carbon atoms (such as acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl, and octadecanoyl).

In formula (1), examples of the arylcarbonyl group for R¹ to R⁶ include arylcarbonyl groups having 7 to 11 carbon atoms (such as benzoyl and naphthoyl).

In formula (1), examples of the alkoxycarbonyl group for R¹ to R⁶ include straight or branched chain alkoxycarbonyl groups having 2 to 18 carbon atoms (such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, and octadecyloxycarbonyl).

In formula (1), examples of the aryloxycarbonyl group for R¹ to R⁶ include aryloxycarbonyl groups having 7 to 11 carbon atoms (such as phenoxycarbonyl and naphthoxycarbonyl).

In formula (1), examples of the arylthiocarbonyl group for R¹ to R⁶ include arylthiocarbonyl groups having 7 to 11 carbon atoms (such as phenylthiocarbonyl and naphthylthiocarbonyl).

In formula (1), examples of the acyloxy group for R¹ to R⁶ include straight or branched chain acyloxy groups having 2 to 19 carbon atoms (such as acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octylcarbonyloxy, tetradecylcarbonyloxy, and octadecylcarbonyloxy).

In formula (1), examples of the arylthio group for R¹ to R⁶ include arylthio groups having 6 to 20 carbon atoms (such as phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenylthio, 3-chlorophenylthio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2-hydroxyphenylthio, 4-hydroxyphenylthio, 2-methoxyphenylthio, 4-methoxyphenylthio, 1-naphthylthio, 2-naphthylthio, 4-[4-(phenylthio)benzoyl]phenylthio, 4-[4-(phenylthio)phenoxy]phenylthio, 4-[4-(phenylthio)phenyl]phenylthio, 4-(phenylthio)phenylthio, 4-benzoylphenylthio, 4-benzoyl-2-chlorophenylthio, 4-benzoyl-3-chlorophenylthio, 4-benzoyl-3-methylthiophenylthio, 4-benzoyl-2-methylthiophenylthio, 4-(4-methylthiobenzoyl)phenylthio, 4-(2-methylthiobenzoyl)phenylthio, 4-(p-methylbenzoyl)phenylthio, 4-(p-ethylbenzoyl)phenylthio, 4-(p-isopropylbenzoyl)phenylthio, and 4-(p-tert-butylbenzoyl)phenylthio).

In formula (1), examples of the alkylthio group for R¹ to R⁶ include straight or branched chain alkylthio groups having 1 to 18 carbon atoms (such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio, dodecylthio, and isooctadecylthio).

In formula (1), examples of the aryl group for R¹ to R⁶ include aryl groups having 6 to 10 carbon atoms (such as phenyl, tolyl, dimethylphenyl, and naphthyl).

In formula (1), examples of the heterocyclic hydrocarbon group for R¹ to R⁶ include heterocyclic hydrocarbon groups having 4 to 20 carbon atoms (such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, indolyl, benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxathiinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, and dibenzofuranyl).

In formula (1), examples of the aryloxy group for R¹ to R⁶ include aryloxy groups having 6 to 10 carbon atoms (such as phenoxy and naphthyloxy).

In formula (1), examples of the alkylsulfinyl group for R¹ to R⁶ include straight or branched chain alkylsulfinyl groups having 1 to 18 carbon atoms (such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, octylsulfinyl, and isooctadecylsulfinyl).

In formula (1), examples of the arylsulfinyl group for R¹ to R⁶ include arylsulfinyl groups having 6 to 10 carbon atoms (such as phenylsulfinyl, tolylsulfinyl, and naphthylsulfinyl).

In formula (1), examples of the alkylsulfonyl group for R¹ to R⁶ include straight or branched chain alkylsulfonyl groups having 1 to 18 carbon atoms (such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl, octylsulfonyl, and octadecylsulfonyl).

In formula (1), examples of the arylsulfonyl group for R¹ to R⁶ include arylsulfonyl groups having 6 to 10 carbon atoms (such as phenylsulfonyl, tolylsulfonyl (tosyl group), and naphthylsulfonyl).

In formula (1), examples of the hydroxy(poly) alkyleneoxy group for R¹ to R⁶ include hydroxy(poly)alkyleneoxy groups represented by formula (2):

HO(-AO)q-  (2)

[wherein AO represents an ethyleneoxy group and/or a propyleneoxy group, and q represents an integer of 1 to 5].

In formula (1), examples of the amino group for R¹ to R⁶ include an amino group (—NH₂) and substituted amino groups having 1 to 15 carbon atoms (such as methylamino, dimethylamino, ethylamino, methylethylamino, diethylamino, n-propylamino, methyl-n-propylamino, ethyl-n-propylamino, n-propylamino, isopropylamino, isopropylmethylamino, isopropylethylamino, diisopropylamino, phenylamino, diphenylamino, methylphenylamino, ethylphenylamino, n-propylphenylamino, and isopropylphenylamino).

In formula (1), examples of the halogen atom for R¹ to R⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In formula (1), R¹ to R⁶ are independent of one another and therefore may be the same as or different from one another.

R¹ to R⁶ each preferably represent an alkyl group, an alkoxy group, an alkylcarbonyl group, or a halogen atom, and in particular, preferably represent a methyl group, a methoxy group, or an acetyl group.

In formula (1), m¹ to m⁶ each represent the number of occurrences of each of R¹ to R⁶, m¹, m⁴, and m⁶ each represent an integer of 0 to 5, preferably 0 to 3, more preferably 0 to 2, in particular, preferably 0 or 1. In formula (1), m², m³, and m⁵ each represent an integer of 0 to 4, preferably 0 to 3, more preferably 0 to 2, in particular, preferably 0 or 1. When m¹ to m⁶ are each in the preferred range, the sulfonium salt will have higher photosensitivity. Preferred specific examples of the sulfonium represented by formula (1) are shown below.

In particular, the sulfonium represented by formula (1) preferably has the structure shown below in view of photosensitivity.

In formula (1), X⁻ represents an anion corresponding to an acid (HX) which is produced by irradiating the sulfonium salt of the invention with an active energy ray (such as visible light, an ultraviolet ray, an electron beam, or an X-ray). X⁻ is not restricted, as long as it represents a monovalent polyatomic anion. X⁻ preferably represents an anion represented by MY_(a) ⁻, (Rf)_(b)PF_(6-b) ⁻, R¹⁰ _(c)BY_(4-c) ⁻, R¹⁰ _(c)GaY_(4-c) ⁻, R¹¹SO₃ ⁻, (R¹¹SO₂)₃C⁻ or (R¹¹SO₂)₂N⁻.

M represents a phosphorus atom, a boron atom, or an antimony atom.

Y represents a halogen atom (preferably a fluorine atom).

Rf represents an alkyl group (preferably an alkyl group having 1 to 8 carbon atoms) 80% by mole or more of whose hydrogen atoms are substituted with fluorine atoms. Examples of the alkyl group to be substituted with fluorine for Rf include straight chain alkyl groups (such as methyl, ethyl, propyl, butyl, pentyl, and octyl), branched alkyl groups (such as isopropyl, isobutyl, sec-butyl, and tert-butyl) and cycloalkyl groups (such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl). The ratio at which the hydrogen atoms of these alkyl groups are substituted with fluorine atoms in Rf is preferably 80% by mole or more, more preferably 90% by mole or more, in particular, preferably 100% by mole, based on the molar number of the hydrogen atoms in the original alkyl group. When the fluorine atom substitution ratio is in the preferred ranges, the sulfonium salt will have higher photosensitivity. In particular, preferred examples of Rf include CF₃—, CF₃CF₂—, (CF₃)₂CF—, CF₃CF₂CF₂—, CF₃CF₂CF₂CF₂—, (CF₃)₂CFCF₂—, CF₃CF₂ (CF₃) CF—, and (CF₃)₃C—. The number of occurrences b of Rf are independent of one another and therefore may be the same as or different from one another.

P represents a phosphorus atom, and F represents a fluorine atom.

R¹⁰ represents a phenyl group whose hydrogen atoms are partially substituted with at least one element or electron-withdrawing group. For example, such one element includes a halogen atom, examples of which include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the electron-withdrawing group include a trifluoromethyl group, a nitro group, and a cyano group. Among them, preferred is a phenyl group one of whose hydrogen atoms is substituted with a fluorine atom or a trifluoromethyl group. The number of occurrences c of R¹⁰ groups are independent of one another and therefore may be the same as or different from one another.

B represents a boron atom, and Ga represents a gallium atom.

K represents an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, wherein the alkyl group and the perfluoroalkyl group may each be any of a straight chain, a branched chain, or a cyclic group, and the aryl group may be substituted or unsubstituted.

S represents a sulfur atom, O represents an oxygen atom, C represents a carbon atom, and N represents a nitrogen atom.

a represents an integer of 4 to 6.

b preferably represents an integer of 1 to 5, more preferably 2 to 4, in particular, preferably 2 or 3.

c preferably represents an integer of 1 to 4, more preferably 4.

Examples of the anion represented by MY_(a) ⁻ include anions represented by SbF₆ ⁻, PF₆ ⁻, and BF₄ ⁻.

Examples of the anion represented by (Rf)_(b)PF_(6-b) ⁻ include anions represented by (CF₃CF₂)₂PF₄ ⁻, (CF₃CF₂)₃PF₃ ⁻, ((CF₃)₂CF)₂PF₄ ⁻, ((CF₃)₂CF)₃PF₃ ⁻, (CF₃CF₂CF₂)₂PF₄ ⁻, (CF₃CF₂CF₂)₃PF₃ ⁻, ((CF₃)₂CFCF₂)₂PF₄ ⁻, ((CF₃)₂CFCF₂)₃PF₃ ⁻, (CF₃CF₂CF₂CF₂)₂PF₄ ⁻, and (CF₃CF₂CF₂CF₂)₃PF₃ ⁻. Among them, preferred are anions represented by (CF₃CF₂)₃PF₃ ⁻, (CF₃CF₂CF₂)₃PF₃ ⁻, ((CF₃)₂CF)₃PF₃ ⁻, ((CF₃)₂CF)₂PF₄ ⁻, ((CF₃)₂CFCF₂)₃PF₃ ⁻, and ((CF₃)₂CFCF₂)₂PF₄ ⁻.

Examples of the anion represented by R¹⁰ _(c)BY_(4-c) ⁻ include anions represented by (C₆F₅)₄B⁻, ((CF₃)₂C₆H₃)₄B⁻, (CF₃C₆H₄)₄B⁻, (C₆F₅)₂BF₂ ⁻, C₆F₅BF₃ ⁻, and (C₆H₃F₂)₄B⁻. Among them, preferred are anions represented by (C₆F₅)₄B⁻ and ((CF₃)₂C₆H₃)₄B⁻.

Examples of the anion represented by R¹⁰ _(c)GaY_(4-c) ⁻ include anions represented by (C₆F₅)₄Ga⁻, ((CF₃)₂C₆H₃)₄Ga⁻, (CF₃C₆H₄)₄Ga⁻, (C₆F₅)₂GaF₂ ⁻, C₆F₅GaF₃ ⁻, and (C₆H₃F₂)₄Ga⁻. Among them, preferred are anions represented by (C₆F₅)₄Ga⁻ and ((CF₃)₂C₆H₃)₄Ga⁻.

Examples of the anion represented by R¹¹SO₃ ⁻ include trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, heptafluoropropanesulfonate anion, nonafluorobutanesulfonate anion, pentafluorophenylsulfonate anion, p-toluenesulfonate anion, benzenesulfonate anion, camphorsulfonate anion, methanesulfonate anion, ethanesulfonate anion, propanesulfonate anion, and butanesulfonate anion. Among them, preferred are trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, butanesulfonate anion, benzenesulfonate anion, and p-toluenesulfonate anion.

Examples of the anion represented by (R¹¹SO₂)₃C⁻ include anions represented by (CF₃SO₂)₃C⁻, (C₂F₅SO₂)₃C⁻, (C₃F₇SO₂)₃C⁻, and (C₄F₉SO₂)₃C⁻.

Examples of the anion represented by (R¹¹SO₂)₂N⁻ include anions represented by (CF₃SO₂)₂N⁻, (C₂F₅SO₂)₂N⁻, (C₃F₇SO₂)₂N⁻, and (C₄F₉SO₂)₂N⁻.

Examples of the monovalent polyatomic anion that may be used include not only anions represented by MY_(a) ⁻, (Rf)_(b)PF_(6-b) ⁻, R¹⁰ _(c)By_(4-c) ⁻, R¹⁰ _(c)GaY_(4-c) ⁻, R¹¹SO₃ ⁻, (R¹¹SO₂)₃C⁻ or (R¹¹SO₂)₂N⁻ but also perhalogenate ions (such as ClO₄ ⁻ and BrO₄ ⁻) halogenated sulfonate ions (such as FSO₃ ⁻ and ClSO₃ ⁻), sulfate ions (such as CH₃SO₄ ⁻, CF₃SO₄ ⁻ and HSO₄ ⁻) carbonate ions (such as HCO₃ ⁻ and CH₃CO₃ ⁻) aluminate ions (such as AlCl₄ ⁻ and AlF₄ ⁻) hexafluoro bismuthate ion (BiF₆ ⁻) carboxylate ions (such as CH₃COO⁻, CF₃COO⁻, C₆H₅COO⁻, CH₃C₆H₄COO⁻, C₆F₅COO⁻ and CF₃C₆H₄COO⁻), arylborate ions (such as B(C₆H₅)₄ ⁻ and CH₃CH₂CH₂CH₂B(C₆H₅)₃ ⁻), thiocyanate ion (SCN⁻), and nitrate ion (NO₃ ⁻).

In view of cationic polymerizability, X⁻ preferably represents anions represented by MY_(a) ⁻, (Rf)_(b)PF_(6-b) ⁻, R¹⁰ _(c)BY_(4-c) ⁻, R¹⁰ _(c)GaY_(4-c) ⁻, and (R¹¹SO₂)₃C⁻, in particular, preferably represents SbF₆ ⁻, PF₆ ⁻, (CF₃CF₂)₃PF₃ ⁻, (C₆F₅)₄B⁻, (CF₃)₂C₆H₃)₄B⁻, (C₆F₅)₄Ga⁻, (CF₃)₂C₆H₃)₄Ga⁻, and (CF₃SO₂)₃C⁻.

When the sulfonium salt is used in a chemically amplified positive photoresist composition, the anion is preferably MY_(a) ⁻, (Rf)_(b)PF_(6-b) ⁻, R¹⁰ _(c)BY_(4-c) ⁻, R¹⁰ _(c)GaY_(4-c) ⁻, R¹¹SO₃ ⁻, (R¹¹SO₂)₃C⁻ or (R¹¹SO₂)₂N⁻, more preferably SbF₆ ⁻, PF₆ ⁻, (CF₃CF₂)₃PF₃ ⁻, (C₆F₅)₄B⁻, (CF₃)₂C₆H₃)₄B⁻, (C₆F₅)₄Ga⁻, (CF₃)₂C₆H₃)₄Ga⁻, trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, butanesulfonate anion, benzenesulfonate anion, p-toluenesulfonate anion, (CF₃SO₂)₃C⁻, or (CF₃SO₂)₂N⁻ in terms of providing good resist resolution or good pattern shape, in particular, preferably (CF₃CF₂)₃PF₃ ⁻, nonafluorobutanesulfonate anion, (C₆F₅)₄B⁻, or ((CF₃)₂C₆H₃)₄B⁻ in view of good compatibility with resist compositions.

The same applies to the case where the sulfonium salt is used in a chemically amplified negative photoresist composition.

Preferred examples of the sulfonium salt of the invention represented by formula (1) include, but are not limited to, those shown below.

(a) The sulfonium salt in which R³ and R⁴ are each a methyl group or a methoxy group, m³ and m⁴ are each 1, and m¹, m², m⁵, and m⁶ are each 0.

(b) The sulfonium salt in which m¹ to m⁶ are all 0.

Preferred specific examples of the sulfonium salt of the invention represented by formula (1) include

-   [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsolfonium     tris(pentafluoroethyl)trifluorophosphate, -   [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium     tetrakis(pentafluorophenyl)borate, -   [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium     hexafluoroantimonate, -   [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium     hexafluorophosphate, -   [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium     trifluoromethanesulfonate, -   [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium     nonafluorobutanesulfonate, -   [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium     methanesulfonate, -   [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium     butanesulfonate, and -   [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium     p-toluenesulfonate.

The sulfonium salt of the invention may be produced by Production Process (1) described below.

<Production Process (1)>

The process shown by the reaction formula below (for example, the process described in Jikken Kagaku Koza (Lectures of Experimental Chemistry), 4th Edition, vol. 24, p. 376, published by Maruzen Co., Ltd. (1992), JP-A No. 07-329399, JP-A No. 08-165290, JP-A No. 10-212286, or JP-A No. 10-7680).

In the above reaction formula, R¹ to R⁶, S, O, X⁻, and m¹ to m⁶ have the same definitions as those in formula (1). H represents a hydrogen atom.

HX′ represents the conjugate acid of a monovalent polyatomic anion. In view of availability, acid stability, and reaction yield, HX′ is preferably methanesulfonic acid, perfluoromethanesulfonic acid, or sulfuric acid.

The dehydrating agent represents, for example, phosphoric anhydride, acetic anhydride, concentrated sulfuric acid, or the like.

The monovalent polyatomic anion (X′⁻) can be replaced with another anion (X⁻) according to the invention, for example, by a metathesis reaction as shown above.

DX represents a salt of an alkali metal (such as lithium, sodium, or potassium) cation with another anion according to the invention (such as an anion represented by MY_(a) ⁻, (Rf)_(b)PF_(6-b) ⁻, R¹⁰ _(c)BY_(4-c) ⁻, R¹⁰ _(c)GaY_(4-c) ⁻, R¹¹SO₃ ⁻, (R¹¹SO₂)₃C⁻ or (R¹¹SO₂)₂N⁻).

DX′ represents a salt of an alkali metal (such as lithium, sodium, or potassium) cation with a monovalent polyatomic anion (such as methanesulfonate anion, perfluoromethanesulfonate anion, or hydrogensulfate anion).

In the above reaction formula, the first step reaction may be performed in the absence of a solvent, or if necessary, may be performed in an organic solvent (such as acetonitrile, tetrahydrofuran, dioxane, ethanol, or acetone). The reaction temperature may be about 20 to 105° C. The reaction time may be about 1 to several tens of hours.

The second step reaction may be performed continuously after the first step or performed after a reaction intermediate (G3) is isolated (and purified if necessary). The reaction intermediate (G3) is mixed and stirred with an aqueous solution of the salt (DX) of an alkali metal cation with a monovalent polyatomic anion so that it is subjected to a metathesis reaction, and the precipitated solid is separated by filtration, or the separated oil product is extracted with an organic solvent, and the solvent is removed, so that the sulfonium salt of the invention is obtained in the form of a solid or a viscous liquid. If necessary, the resulting solid or viscous liquid may be purified by washing with an appropriate organic solvent, recrystallization technique, or column chromatography (the same applies hereinafter).

Starting materials (G1) and (G2) used in the above production process can be obtained by known methods, for example, using the reactions described in Bulletin of the Chemical Society of Japan, 53, 1385-1389 (1980) and the like or the oxidation reaction described in Jikken Kagaku Koza (Lectures of Experimental Chemistry), 4th Edition, vol. 23, pp. 276-277, published by Maruzen Co., Ltd. (1991).

The chemical structure of the sulfonium salt of the invention can be identified by a common analysis method or methods (such as ¹H-, ¹¹B-, ¹³C-, ¹⁹F-, ³¹P-nuclear magnetic resonance spectroscopy, infrared absorption spectroscopy, and/or elemental analysis).

The mixed sulfonium salt of the invention comprises the sulfonium salt represented by formula (1) described above and the sulfonium salt represented by formula (2) described below.

Use of the mixed sulfonium salt makes it possible to further improve sensitivity and the patterned shape of the resist composition.

[In formula (2), R¹ to R⁹ each independently represent an alkyl group, a hydroxyl group, an alkoxyl group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, m¹ to m⁹ each represent the number of occurrences of each of R¹ to R⁹, m⁴, m⁶, m⁷, and m⁹ each represent an integer of 0 to 5, m¹, m², m³, m⁵ and each represent an integer of 0 to 4, and X⁻ represents a monovalent polyatomic anion].

Examples of the alkyl group, the hydroxyl group, the alkoxyl group, the alkylcarbonyl group, the arylcarbonyl group, the alkoxycarbonyl group, the aryloxycarbonyl group, the arylthiocarbonyl group, the acyloxy group, the arylthio group, the alkylthio group, the aryl group, the heterocyclic hydrocarbon group, the aryloxy group, the alkylsulfinyl group, the arylsulfinyl group, the alkylsulfonyl group, the arylsulfonyl group, the hydroxy(poly)alkyleneoxy group, the optionally substituted amino group, the cyano group, the nitro group, or the halogen atom described above are the same as those listed for formula (1).

R¹ to R⁹ are independent of one another and therefore may be the same as or different from one another.

In the formula, m¹ to m⁹ each represent the number of occurrences of each of R¹ to R⁹, m⁴, m⁶, m⁷, and m⁹ each represent an integer of 0 to 5, preferably 0 to 3, more preferably 0 to 2, in particular, preferably 0 or 1, and m¹, m², m³, m⁵, and m⁸ each represent an integer of 0 to 4, preferably 0 to 3, more preferably 0 to 2, in particular, preferably 0 or 1. When m¹ to m⁶ are each in the preferred range, the sulfonium salt will have higher photosensitivity.

Preferred specific examples of the cation of the sulfonium salt represented by formula (2) are shown below.

In particular, the cation of the sulfonium salt represented by formula (2) preferably has the structure shown below in view of photosensitivity.

In formula (2), X⁻ represents a monovalent polyatomic anion, examples of which include the same as those listed for formula (1).

Preferred specific examples of the sulfonium salt of the invention represented by formula (2) include

-   phenyl[4-[4-(4′-phenylbiphenylylsulfonio)     biphenylylthio]phenyl]-4-biphenylylsulfonium     bis[tris(pentafluoroethyl)trifluorophosphate], -   phenyl[4-[4-(4′-phenylbiphenylylsulfonio)     biphenylylthio]phenyl]-4-biphenylylsulfonium     bis[tetrakis(pentafluorophenyl) borate], -   phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium     bis(hexafluoroantimonate), -   phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium     bis(hexafluorophosphate), -   phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium     bis(trifluoromethanesulfonate), -   phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium     bis(nonafluorobutanesulfonate), -   phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium     bis(methanesulfonate), -   phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium     bis(butanesulfonate), and     biphenylyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio] -   phenyl]-4-biphenylylsulfonium bis(p-toluenesulfonate).

Based on the total amount (100% by mole) of the sulfonium salt represented by formula (1) and the sulfonium salt represented by (2), the content of the sulfonium salt represented by formula (1) is preferably from 50 to 99.9% by mole, more preferably from 70 to 99.9% by mole, even more preferably from 80 to 99.9% by mole. If the content of the sulfonium salt of formula (1) is less than 50% by mole, the sulfonium salt may have low thermal stability, so that the resulting formulation with a cationically polymerizable compound or the resulting positive and negative photoresist compositions may have low storage stability. While the sulfonium salt of formula (2) serves to increase photocurability or improve the patterned shape of the resist composition, the formulation rate of the salt has no clear lower limit and may be 0.1% by mole or more, 1% by mole or more, or 5% by mole or more.

The sulfonium salt mixture of the invention may be produced by a process similar to production process (1) described above. The ratio between the sulfonium salt of <formula (1)> and the sulfonium salt of <formula (2)> described above can be adjusted by controlling the ratio between the sulfide <G1> and the sulfoxide <G2> as the starting materials. If the sulfoxide is used in an excess molar ratio relative to the sulfide, the product ratio of <formula (2)> will be high. If the sulfoxide is used in a low molar ratio relative to the sulfide, the product ratio of <formula (1)> will be high.

The sulfonium salt or the mixed sulfonium salt of the invention is suitable as a photo-acid generator.

The photo-acid generator refers to an agent whose chemical structure is decomposed by irradiation with light to generate an acid. The generated acid can be used as a catalyst for an epoxide curing reaction or the like, or used to make a chemically amplified positive photoresist composition soluble in an alkali developer, or used to facilitate the crosslinking reaction of a base resin with a crosslinking agent in a chemically amplified negative photoresist composition so that the composition can be made insoluble in an alkali developer.

To form the photo-acid generator of the invention, the sulfonium salt of the invention or the sulfonium salt mixture of the invention may be used as it is or in combination with an additional photo-acid generator.

When an additional photo-acid generator is contained, the content (% by mole) of the additional photo-acid generator is preferably from 1 to 100, more preferably from 5 to 50, based on the total molar number of the sulfonium salt(s) of the invention.

Examples of the additional photo-acid generator include conventionally known ones such as onium salts (such as sulfonium, iodonium, selenium, ammonium, and phosphonium) and salts of transition metal complex ions with anions.

The photo-acid generator of the invention may be previously dissolved in a solvent that does not inhibit cationic polymerization, so that it can be easily dissolved in a cationically polymerizable compound.

Examples of the solvent include carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, and diethyl carbonate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; polyhydric alcohols and derivatives thereof, such as monomethyl ethers, monoethyl ethers, monopropyl ethers, monobutyl ethers, or monophenyl ethers of ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and dipropylene glycol monoacetate; cyclic ethers such as dioxane; esters such as ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate; and aromatic hydrocarbons such as toluene and xylene.

When a solvent is used, the amount of the solvent used is preferably from 15 to 1,000 parts by weight, more preferably from 30 to 500 parts by weight, based on 100 parts by weight of the photo-acid generator of the invention. A single solvent may be used alone or two or more solvents may be used in combination.

The energy ray-curable composition of the invention comprises the above photo-acid generator and a cationically polymerizable compound.

Examples of the cationically polymerizable compound include cyclic ethers (such as epoxide and oxetane), ethylenically unsaturated compounds (such as vinyl ether and styrene), bicycloorthoesters, spiroorthocarbonates, and spiroorthoesters (such as those described in JP-A No. 11-060996, JP-A No. 09-302269, JP-A No. 2003-026993, JP-A No. 2002-206017, JP-A No. 11-349895, JP-A No. 10-212343, JP-A No. 2000-119306, JP-A No. 10-67812, JP-A No. 2000-186071, JP-A No. 08-85775, JP-A No. 08-134405, JP-A No. 2008-20838, JP-A No. 2008-20839, JP-A No. 2008-20841, JP-A No. 2008-26660, JP-A No. 2008-26644, JP-A No. 2007-277327, “Photopolymer Handbook” edited by The Technical Association of Photopolymers, Japan (1989, Kogyo Chosakai Publishing, Co., Ltd.), “UV/EB Koka Gijutsu” (Technology of UV/EB Curing), edited by Sogo Gijutsu Center (1982, Sogo Gijutsu Center), “UV/EB Koka Zairyo” (UV/EB Curable Materials), edited by RadTech Japan (1992, CMC), “UV-Koka niokeru Koka-Furyo/Sogai-Genin to Sonotaisaku” (Causes of UV Curing Defects/Inhibition and Countermeasures Therefor), edited by TECHNICAL INFORMATION INSTITUTE (2003, TECHNICAL INFORMATION INSTITUTE CO., LTD.), Journal of the Japan Society of Colour Material, 68, (5), 286-293 (1995), and Fine Chemical, 29, (19), 5-14 (2000)).

Known epoxides and the like may be used as epoxides, example of which include aromatic epoxides, alicyclic epoxides, and aliphatic epoxides.

Examples of the aromatic epoxides include glycidyl ethers of monohydric or polyhydric phenols having at least one aromatic ring (such as phenol, bisphenol A, phenol novolac, and alkylene oxide adducts thereof).

Examples of the alicyclic epoxides include compounds obtained by epoxidation of compounds having at least one cyclohexene or cyclopentene ring with an oxidizing agent (such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate).

Examples of the aliphatic epoxides include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof (such as 1,4-butanediol diglycidyl ether and 1,6-hexanediol diglycidyl ether), polyglycidyl esters of aliphatic polybasic acids (such as diglycidyl tetrahydrophthalate), and epoxidized long-chain unsaturated compounds (such as epoxidized soybean oil and epoxidized polybutadiene).

Known oxetanes and the like may be used as oxetanes, examples of which include 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyl(3-ethyl-3-oxetanylmethyl)ether, 2-hydroxyethyl(3-ethyl-3-oxetanylmethyl)ether, 2-hydroxypropyl(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, oxetanylsilsesquioxetane, and phenol novolac oxetane.

Known cationically polymerizable monomers and the like may be used as ethylenically unsaturated compounds, examples of which include aliphatic monovinyl ethers, aromatic monovinyl ethers, polyfunctional vinyl ethers, styrenes, and cationically polymerizable nitrogen-containing monomers.

Examples of the aliphatic monovinyl ethers include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether.

Examples of the aromatic monovinyl ethers include 2-phenoxyethyl vinyl ether, phenyl vinyl ether, and p-methoxyphenyl vinyl ether.

Examples of the polyfunctional vinyl ethers include butanediol-1,4-divinyl ether and triethylene glycol divinyl ether.

Examples of the styrenes include styrene, α-methylstyrene, p-methoxystyrene, and p-tert-butoxystyrene.

Examples of the cationically polymerizable nitrogen-containing monomers include N-vinylcarbazole and N-vinylpyrrolidone.

Examples of the bicycloorthoesters include 1-phenyl-4-ethyl-2,6,7-trioxabicyclo[2.2.2]octane and 1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo[2.2.2]octane.

Examples of the spiroorthocarbonates include 1,5,7,11-tetraoxaspiro[5.5]undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro[5.5]undecane.

Examples of the spiroorthoesters include 1,4,6-trioxaspiro[4.4]nonane, 2-methyl-1,4,6-trioxaspiro[4.4]nonane, and 1,4,6-trioxaspiro[4.5]decane.

Among these cationically polymerizable compounds, epoxides, oxetanes, and vinyl ethers are preferred, epoxides and oxetane are more preferred, and alicyclic epoxides and oxetanes are particularly preferred. These cationically polymerizable compounds may be used alone or in combination of two or more.

The content of the photo-acid generator of the invention in an energy ray-curable composition is preferably from 0.05 to 20 parts by weight, more preferably from 0.1 to 10 parts by weight, based on 100 parts by weight of the cationically polymerizable compound. Within the range, the cationically polymerizable compound can be more sufficiently polymerized, so that the physical properties of the cured product can be further improved. It will be understood that the content may be determined taking into account various factors such as the properties of the cationically polymerizable compound, the type and irradiation dose of the energy ray, the temperature, the curing time, the humidity, and the thickness of the coating film, and is not limited to the above range.

If necessary, the energy ray-curable composition of the invention may contain known additives (such as a sensitizer, a pigment, a filler, an antistatic agent, a flame retardant, an anti-foaming agent, a fluidity controlling agent, a light stabilizer, an antioxidant, a tackifier, an ion scavenger, an anti-coloring agent, a solvent, a nonreactive resin, and a radically-polymerizable compound).

The energy ray-curable composition of the invention basically does not need any sensitizer, but if necessary, it may contain a sensitizer as a material for complementing the curability. Known sensitizers (such as those described in JP-A No. 11-279212 and JP-A No. 09-183960) and the like may be used as such a sensitizer, examples of which include anthracenes {such as anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, and 9,10-dipropoxyanthracene}; pyrene; 1,2-benzanthracene; perylene; tetracene; coronene; thioxanthones {such as thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone}; phenothiazine {such as phenothiazine, N-methylphenothiazine, N-ethylphenothiazine, and N-phenylphenothiazine}; xanthone; naphthalenes {such as 1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dihydroxynaphthalene, and 4-methoxy-1-naphthol}; ketones {such as dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, and 4-benzoyl-4′-methyldiphenylsulfide}; carbazoles {such as N-phenylcarbazole, N-ethylcarbazole, poly-N-vinylcarbazole, and N-glycidylcarbazole}; chrysenes {such as 1,4-dimethoxychrysene and 1,4-di-α-methylbenzyloxychrysene}; and phenanthrenes {such as 9-hydroxyphenanthrene, 9-methoxyphenanthrene, 9-hydroxy-10-methoxyphenanthrene, and 9-hydroxy-10-ethoxyphenanthrene}.

When a sensitizer is contained, the content of the sensitizer is preferably from 1 to 300 parts by weight, more preferably from 5 to 200 parts by weight, based on 100 parts of the photo-acid generator.

Known pigments and the like may be used as pigments, examples of which include inorganic pigments (such as titanium oxide, iron oxide, and carbon black) and organic pigments (such as azo pigments, cyanine pigments, phthalocyanine pigments, and quinacridone pigments).

When a pigment is contained, the content of the pigment is preferably from 0.5 to 400,000 parts by weight, more preferably from 10 to 150,000 parts by weight, based on 100 parts of the photo-acid generator.

Known fillers and the like may be used as fillers, examples of which include fused silica, crystalline silica, calcium carbonate, aluminum oxide, aluminum hydroxide, zirconium oxide, magnesium carbonate, mica, talc, calcium silicate, and lithium aluminum silicate.

When a filler is contained, the content of the filler is preferably from 50 to 600,000 parts by weight, more preferably 300 to 200,000 parts by weight, based on 100 parts of the photo-acid generator.

Known antistatic agents and the like may be used as antistatic agents, examples of which include nonionic antistatic agents, anionic antistatic agents, cationic antistatic agents, ampholytic antistatic agents, and high molecular weight antistatic agents.

When an antistatic agent is contained, the content of the antistatic agent is preferably from 0.1 to 20,000 parts by weight, more preferably from 0.6 to 5,000 parts by weight, based on 100 parts of the photo-acid generator.

Known flame retardants and the like may be used as flame retardants, examples of which include inorganic flame retardants {such as antimony trioxide, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium metaborate, red phosphorus, aluminum hydroxide, magnesium hydroxide, and calcium aluminate}; bromine flame retardants {such as tetrabromophthalic anhydride, hexabromobenzene, and decabromobiphenyl ether}; and phosphate flame retardants {such as tris(tribromophenyl) phosphate}.

When a flame retardant is contained, the content of the flame retardant is preferably from 0.5 to 40,000 parts by weight, more preferably from 5 to 10,000 parts by weight, based on 100 parts of the photo-acid generator.

Known anti-foaming agents and the like may be used as anti-foaming agents, examples of which include alcoholic anti-foaming agents, metallic soap anti-foaming agents, phosphate anti-foaming agents, fatty acid ester anti-foaming agents, polyether anti-foaming agents, silicone anti-foaming agents, and mineral oil anti-foaming agents.

Known fluidity controlling agents and the like may be used as fluidity controlling agents, examples of which include hydrogenated castor oil, oxidized polyethylene, organic bentonite, colloidal silica, amide wax, metallic soap, and acrylic ester polymers.

Known light stabilizers and the like may be used as light stabilizers, examples of which include ultraviolet absorbing stabilizers {such as benzotriazole, benzophenone, salicylates, cyanoacrylates, and derivatives thereof}; radical scavenging stabilizers {such as hindered amines}; and quenching stabilizers {such as nickel complexes}.

Known antioxidants and the like may be used as antioxidants, examples of which include phenolic antioxidants (such as monophenolic, bisphenolic, and macromolecular phenolic antioxidants), sulfur-based antioxidants, and phosphorus-based antioxidants.

Known tackifiers and the like may be used as tackifiers, example of which include coupling agents, silane coupling agents, and titanium coupling agents.

Known ion scavenger and the like may be used as ion scavenger, examples of which include organoaluminum (such as alkoxyaluminum and phenoxyaluminum).

Known anti-coloring agents and the like may be used as anti-coloring agents, and antioxidants are generally effective, examples of which include phenolic antioxidants (such as monophenolic, bisphenolic, and macromolecular phenolic antioxidants), sulfur-based antioxidants, and phosphorus-based antioxidants.

When an anti-foaming agent, a fluidity controlling agent, a light stabilizer, an antioxidant, a tackifier, an ion scavenger, or an anti-coloring agent is contained, the content of each material is preferably from 0.1 to 20,000 parts by weight, more preferably from 0.5 to 5,000 parts by weight, based on 100 parts of the photo-acid generator.

Any solvent that can be used to dissolve the cationically polymerizable compound or to control the viscosity of the energy ray-curable composition may be used as solvents, examples of which include those listed for the above photo-acid generator.

When a solvent is contained, the content of the solvent is preferably from 50 to 2,000,000 parts by weight, more preferably from 200 to 500,000 parts by weight, based on 100 parts of the photo-acid generator.

Examples of the nonreactive resin include polyester, polyvinyl acetate, polyvinyl chloride, polybutadiene, polycarbonate, polystyrene, polyvinyl ether, polyvinyl butyral, polybutene, hydrogenated styrene-butadiene block copolymers, copolymers of (meth) acrylic acid esters, and polyurethane. The number average molecular weight of these resins is preferably from 1,000 to 500,000, more preferably from 5,000 to 100,000 (the number average molecular weight is a value measured by a general method such as GPC).

When a nonreactive resin is contained, the content of the nonreactive resin is preferably from 5 to 400,000 parts by weight, more preferably from 50 to 150,000 parts by weight, based on 100 parts of the photo-acid generator.

When a nonreactive resin is contained, it is preferably dissolved in advance in a solvent so that it can be easily dissolved in the cationically polymerizable compound or the like.

Known radically-polymerizable compounds and the like may be used as radically-polymerizable compounds {such as those described in “Photopolymer Handbook” edited by The Technical Association of Photopolymers, Japan (1989, Kogyo Chosakai Publishing, Co., Ltd.), “UV/EB Koka Gijutsu” (Technology of UV/EB Curing), edited by Sago Gijutsu Center (1982, Sago Gijutsu Center), “UV/EB Koka Zairyo” (UV/EB Curable Materials), edited by RadTech Japan (1992, CMC), and “UV-Koka niokeru Koka-Furyo/Sogai-Genin to Sonotaisaku” (Causes of UV Curing Defects/Inhibition and Remedies Therefor), edited by TECHNICAL INFORMATION INSTITUTE (2003, TECHNICAL INFORMATION INSTITUTE CO., LTD.)}, examples of which include monofunctional monomers, bifunctional monomers, polyfunctional monomers, epoxy (meth)acrylate, polyester (meth)acrylate, and urethane (meth)acrylate.

When a radically-polymerizable compound is contained, the content of the radically-polymerizable compound is preferably from 5 to 400,000 parts by weight, more preferably from 50 to 150,000 parts by weight, based on 100 parts of the photo-acid generator.

When a radically-polymerizable compound is contained, a radical polymerization initiator initiating polymerization with heat or light is preferably used so that the compound can be polymerized by radical polymerization.

Known radical polymerization initiators and the like may be used as radical polymerization initiators, examples of which include thermal radical polymerization initiators (such as organic peroxides and azo compounds) and photoradical polymerization initiators (such as acetophenone-based initiators, benzophenone-based initiators, Michler's ketone-based initiators, benzoin-based initiators, thioxanthone-based initiators, and acylphosphine-based initiators.

When a radical polymerization initiator is contained, the content of the radical polymerization initiator is preferably from 0.01 to 20 parts by weight, more preferably from 0.1 to parts by weight, based on 100 parts of the radically-polymerizable compound.

The energy ray-curable composition of the invention may be prepared by uniformly mixing and dissolving the cationically polymerizable compound, the photo-acid generator, and if necessary an optional additive(s) at room temperature (about 20 to 30° C.) or if necessary, under heating (about 40 to 90° C.), or by further kneading them with a triple-roll mill or the like.

The energy ray-curable composition of the invention may be cured by irradiation with energy rays so that a cured product can be obtained.

The energy ray may be of any energy ray as long as it has an energy to induce the decomposition of the sulfonium salt of the invention, preferred examples of which include energy rays in the ultraviolet to visible light region (wavelength: from about 100 to about 800 nm) obtained from a low pressure-, medium pressure-, high pressure-, or ultra high pressure-mercury lamp, a metal halide lamp, an LED lamp, a xenon lamp, a carbon arc lamp, a fluorescent lamp, a semiconductor solid-state laser, an argon laser, a He—Cd laser, a KrF excimer laser, an ArF excimer laser, or an F₂ laser. Radiations with a high energy, such as electron beams or X-rays may also be used as the energy rays.

While the energy ray irradiation time is influenced by the intensity of the energy rays or the permeability of the energy rays to the energy ray-curable composition, an energy ray exposure time of about 0.1 to 10 seconds is enough at room temperature (about 20 to 30° C.). However, if the permeability of the energy rays is low or if the thickness of the energy ray-curable composition is large, for example, it is sometimes preferred to spend more time. Most energy ray-curable compositions are cured by cationic polymerization in 0.1 seconds to several minutes after the irradiation with energy rays. If necessary, however, post-curing may be performed by heating at a temperature of room temperature (about 20 to 30° C.) to 150° C. for several seconds to several hours after the irradiation with energy rays.

Specific applications of the energy ray-curable composition of the invention include paint compositions, coating agents, ink compositions, inkjet ink compositions, positive resists, resist films, liquid resists, negative resists, MEMS resists, positive photosensitive materials, negative photosensitive materials, various adhesives, molding materials, casting materials, putty materials, glass fiber impregnating agents, fillers, sealing materials, sealants, optical semiconductor (LED) sealants, optical waveguide materials, nano-imprint materials, stereolithography materials, and micro-stereolithography materials.

The sulfonium salt of the invention, which can generate a strong acid upon irradiation with light, may also be used as a photo-acid generator for known chemically amplified resist materials (such as those described in JP-A No. 2003-267968, JP-A No. 2003-261529, and JP-A No. 2002-193925).

Examples of the chemically amplified resist materials include (1) a two-component chemically amplified positive resist comprising, as essential ingredients, a photo-acid generator and a resin that can be made soluble in an alkali developing solution by the action of an acid; (2) a three-component chemically amplified positive resist comprising, as essential ingredients, a resin soluble in an alkali developing solution, a dissolution inhibitor that can be made soluble in an alkali developing solution by the action of an acid, and a photo-acid generator; and (3) a chemically amplified negative resist comprising, as essential ingredients, a resin soluble in an alkali developing solution, a crosslinking agent that can crosslink the resin to make the resin insoluble in an alkali developing solution when heated in the presence of an acid, and a photo-acid generator.

The chemically amplified positive photoresist composition of the invention contains an ingredient (A) comprising the photo-acid generator of the invention, which is a compound generating an acid when the compound is irradiated with light or a radiation; and a resin ingredient (B) increasing its solubility in an alkali under the action of an acid.

In the chemically amplified positive photoresist composition of the invention, the ingredient (A) may be used in combination with an additional known conventional photo-acid generator. Examples of the additional photo-acid generator include onium salt compounds, sulfone compounds, sulfonate compounds, sulfonimide compounds, disulfonyl diazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, triazine compounds, and nitrobenzyl compounds, as well as organohalogen compounds and disulfone.

The additional known conventional photo-acid generator is preferably at least one from the group of an onium compound, a sulfonimide compound, a diazomethane compound, and an oxime sulfonate compound.

When such an additional known conventional photo-acid generator is used in combination, the amount of the additional photo-acid generator used is generally from 10 to 900 parts by weight, preferably from 25 to 400 parts by weight, based on 100 parts by weight of the total amount of the sulfonium salts represented by general formulae (1) and (2) described above, although the amount thereof may be arbitrary.

The content of the above ingredient (A) is preferably from 0.05 to 5% by weight, in the solids of the chemically amplified positive photoresist composition.

<Resin Ingredient (B) Increasing its Solubility in an Alkali Under the Action of an Acid>

The aforesaid “resin (B) increasing its solubility in an alkali under the action of an acid” (hereinafter referred to as “ingredient (B)” in the description), which is used in the chemically amplified positive photoresist composition of the invention for thick films, is at least one resin selected from the group consisting of a novolac resin (B1), a polyhydroxystyrene resin (B2), and an acrylic resin (B3), or a mixture thereof, or a copolymer thereof.

[Novolac Resin (B1)]

The novolac resin (B1) to be used may be a resin represented by general formula (b1) described below.

In general formula (b1) described above, R^(1b) represents an acid-dissociating solubility-inhibiting group, R^(1b) and R^(3b) each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents the number of repeating units of the structure in the parentheses.

The above acid-dissociating solubility-inhibiting group represented by R^(1b) is preferably a straight chain alkyl group having 1 to 6 carbon atoms, a branched chain alkyl group having 3 to 6 carbon atoms, a cyclic alkyl group having 3 to 6 carbon atoms, a tetrahydropyranyl group, a tetrahydrofuranyl group, or a trialkylsilyl group.

Specific examples of the above acid-dissociating solubility-inhibiting group represented by R^(1b) include a methoxyethyl group, an ethoxyethyl group, a n-propoxyethyl group, an isopropoxyethyl group, a n-butoxyethyl group, an isobutoxyethyl group, a tert-butoxyethyl group, a cyclohexyloxyethyl group, a methoxypropyl group, an ethoxypropyl group, a 1-methoxy-1-methyl-ethyl group, a 1-ethoxy-1-methylethyl group, a tert-butoxycarbonyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl group, and a tri-tert-butyldimethylsilyl group.

[Polyhydroxystyrene Resin (B2)]

The polyhydroxystyrene resin (B2) to be used may be a resin represented by general formula (b4) described below.

In general formula (b4) described above, R^(8b) represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R^(9b) represents an acid-dissociating solubility-inhibiting group, and n represents the number of repeating units of the structure in the parentheses.

The above alkyl group having 1 to 6 carbon atoms may be a straight chain alkyl group having 1 to 6 carbon atoms, a branched chain alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms. Specifically, it may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, or a neopentyl group, and the cyclic alkyl group may be a cyclopentyl group or a cyclohexyl group.

Examples of the above acid-dissociating solubility-inhibiting group represented by R^(9b) which may be used include those listed for R^(1b) described above.

The polyhydroxystyrene resin (B2) may further comprise, as a structural unit, an additional polymerizable compound for properly controlling the physical and chemical properties. Such a polymerizable compound may be a known radically-polymerizable or anionically-polymerizable compound. Examples thereof include monocarboxylic acids such as acrylic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having a carboxyl group and an ester bond, such as 2-methacryloyloxyethylsuccinic acid; alkyl (meth)acrylates such as methyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate; vinyl group-containing aromatic compounds such as styrene and vinyl toluene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; nitrile group-containing polymerizable compounds such as acrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride; and amide bond-containing polymerizable compounds such as acrylamide.

[Acrylic Resin (B3)]

The acrylic resin (B3) to be used may be any of resins represented by general formulae (b5) to (b10) described below.

In general formulae (b5) to (b7) described above, R^(10b) to R^(17b) each independently represent a hydrogen atom, a straight chain alkyl group having 1 to 6 carbon atoms, a branched chain alkyl group having 3 to 6 carbon atoms, a fluorine atom, a straight chain fluorinated alkyl group having 1 to 6 carbon atoms, or a branched chain fluorinated alkyl group having 3 to 6 carbon atoms, X^(b) represents a moiety that forms a hydrocarbon ring of 5 to 20 carbon atoms with the carbon atom bonded to the moiety, Y^(b) represents an optionally substituted aliphatic cyclic group or an optionally substituted alkyl group, n represents the number of repeating units of the structure in the parentheses, p represents an integer of 0 to 4, and q represents 0 or 1.

In general formulae (b8), (b9), and (b10), R^(18b), R^(20b), and R^(21b) each independently represent a hydrogen atom or a methyl group. In general formula (b8), each occurrence of R^(19b) independently represents a hydrogen atom, a hydroxyl group, a cyano group, or a COOR^(23b) group (wherein R^(23b) represents a hydrogen atom, a straight chain alkyl group having 1 to 4 carbon atoms, a branched chain alkyl group having 3 to 4 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms). In general formula (b10), each occurrence of R^(22b) independently represents a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, a straight chain alkyl group having 1 to 4 carbon atoms, or a branched chain alkyl group having 3 to 4 carbon atoms, wherein at least one of R^(22b) is the alicyclic hydrocarbon group or a derivative thereof, or any two of R^(22b), together with the common carbon atom to which they are each bonded, join to form a bivalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, and the remaining R^(22b) moieties are a straight chain alkyl group having 1 to 4 carbon atoms, a branched chain alkyl group having 3 to 4 carbon atoms, or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof.

Among the above ingredients (B), the acrylic resin (B3) is preferably used.

The polystyrene-equivalent weight average molecular weight of the ingredient (B) is preferably from 10,000 to 600,000, more preferably from 50,000 to 600,000, even more preferably from 230,000 to 550,000. When it has such a weight average molecular weight, the resist resin can have excellent physical properties.

The ingredient (B) is also preferably a resin with a dispersity of 1.05 or more. As used herein, the term “dispersity” refers to a value obtained by dividing the weight average molecular weight by the number average molecular weight. When the dispersity is such a value, the resist can have high plating resistance and the resist resin can have excellent physical properties.

The content of the above ingredient (B) is preferably from 5 to 60% by weight, in the solids of the chemically amplified positive photoresist composition.

<Alkali-Soluble Resin (C)>

The chemically amplified positive photoresist composition of the invention preferably further contains an alkali-soluble resin (referred to as “ingredient (C)” in the description) for improving the physical properties of the resist resin. The ingredient (C) is preferably at least one selected from the group consisting of a novolac resin, a polyhydroxystyrene resin, an acrylic resin, and a polyvinyl resin.

The content of the above ingredient (C) is preferably from 5 to 95 parts by weight, more preferably from 10 to 90 parts by weight, based on 100 parts by weight of the above ingredient (B). When it is 5 parts by weight or more, the physical properties of the resist resin can be improved, and if it is 95 parts by weight or less, film loss during development will tend to be prevented.

<Acid Diffusion Controlling Agent (D)>

The chemically amplified positive photoresist composition of the invention for thick films preferably further contains an acid diffusion controlling agent (D) (referred to as “ingredient (D)” in the description) for improving the shape of the resist pattern and post exposure delay time stability. The ingredient (D) is preferably a nitrogen-containing compound, and if necessary, may contain an organic carboxylic acid, or a phosphorous oxo acid or a derivative thereof.

The chemically amplified positive photoresist composition of the invention may further contain an adhesion auxiliary agent for improving adhesion to the substrate. A functional silane coupling agent is preferable as the adhesion auxiliary agent to be used.

The chemically amplified positive photoresist composition of the invention may further contain a surfactant for improving coating properties, anti-foaming properties, leveling properties, or the like.

The chemically amplified positive photoresist composition of the invention may further contain an acid, an acid anhydride, or a high-boiling-point solvent for fine adjustment of its solubility in an alkali developing solution.

The chemically amplified positive photoresist composition of the invention, which does not basically need a sensitizer, may also contain a sensitizer for complementing the sensitivity, if necessary. A known conventional sensitizer may be used as such a sensitizer, specific examples of which include aforesaid sensitizers.

The amount of the sensitizer used may be from 5 to 500 parts by weight, preferably from 10 to 300 parts by weight, based on 100 parts by weight of the total amount of the sulfonium salts represented by general formulae (1) and (2) described above.

Also, the chemically amplified positive photoresist composition of the invention may appropriately contain an organic solvent for adjusting viscosity. Specific examples of the organic solvent include aforesaid solvents.

The amount of the organic solvent used is preferably in such a range that the solids content of the chemically amplified positive photoresist composition of the invention is 30% by weight or more so that a photoresist layer with a thickness of 5 μm or more is obtained using the composition (for example, by spin coating).

For example, the chemically amplified positive photoresist composition of the invention for thick films can be prepared only by mixing or stirring the above ingredients using a conventional method, and if necessary, the ingredients may be dispersed or mixed using a disperser such as a dissolver, a homogenizer, or a three-roll mill. After the mixing, the product may be further filtered using a mesh, a membrane filter, or the like.

The chemically amplified positive photoresist composition of the invention is suitable for forming a photoresist layer with a thickness of generally 5 to 150 μm, more preferably 10 to 120 μm, even more preferably 10 to 100 μm, on a support. The resulting photoresist laminate comprises the support and a photoresist layer that is placed on the support and comprises the chemically amplified positive photoresist composition of the invention.

The support is not particularly limited, and any known conventional support may be used, examples of which include a substrate for electronic parts and a product produced by forming a given wiring pattern on the substrate. Examples of such a substrate include a substrate made of silicon, silicon nitride, or metal such as titanium, tantalum, palladium, titanium-tungsten, copper, chromium, iron, or aluminum, and a glass substrate. In particular, the use of the chemically amplified positive photoresist composition of the invention makes it possible to successfully form a resist pattern even on a copper substrate. Examples of materials that may be used for wiring pattern include copper, solder, chromium, aluminum, nickel, and gold.

For example, the above photoresist laminate may be produced as described below. Specifically, a solution of the chemically amplified positive photoresist composition prepared as described above is applied to the support, and the solvent is removed by heating, so that a desired coating film is formed. The application to the support may be performed by spin coating, slit coating, roll coating, screen printing, applicator method, or any other application method. The coating film of the composition of the invention may be prebaked under the conditions of generally 70 to 150° C., preferably 80 to 140° C., and about 2 to 60 minutes, which depend on the type or formulation rate of each ingredient in the composition, the thickness of the coating, or the like.

The thickness of the photoresist layer may be generally in the range of 5 to 150 μm, preferably 10 to 120 μm, more preferably 10 to 100 μm.

In order to form a resist pattern using the photoresist laminate obtained as described above, the resulting photoresist layer may be site-selectively irradiated with (or exposed to) light or a radiation, such as an ultraviolet ray or visible light with a wavelength of 300 to 500 nm.

As used herein, “light” may be of any type activating the acid generator to generate an acid and are intended to include ultraviolet rays, visible light, or far ultraviolet rays, and “radiations” means X-rays, electron beams, ion beams, or the like. Examples of sources for light or radiations that may be used include low-pressure mercury lamps, high-pressure mercury lamps, ultra high-pressure mercury lamps, metal halide lamps, argon gas lasers, and LED lamps. The irradiation dose may be from 50 to 10,000 mJ/cm², for example, when an ultra high-pressure mercury lamp is used, although the irradiation dose depends on the type or formulation amount of each ingredient in the composition, the thickness of the coating film, or the like.

After the exposure, heating is performed using a known method to enhance the diffusion of the acid, so that the alkali solubility of the exposed part of the photoresist layer is changed. Subsequently, the unnecessary part is dissolved or removed, for example, using a given alkaline aqueous solution as a developer, so that a desired resist pattern is obtained.

While the development time depends on the type or formulation rate of each ingredient in the composition, or the dry coating thickness of the composition, it is generally from 1 to 30 minutes. The development method may be any of a puddle development method, a dipping method, a puddle method, and a spray development method. After the development, washing with flowing water is performed for 30 to 90 seconds, and drying is performed using an air gun, an oven, or the like.

A conductor such as a metal is embedded, for example, by plating or the like, in the non-resist part (where the resist has been removed using the alkali developing solution) of the resist pattern obtained as described above so that a joining terminal such as a metal post or bump can be formed. The plating method is not particularly restricted, and various known conventional plating methods may be used. The plating solution to be used is preferably a solder, copper, gold, or nickel plating solution. The remaining resist pattern is finally removed by a conventional method using a liquid stripper or the like.

The chemically amplified positive photoresist composition of the invention may also be used to form a dry film. Such a dry film comprises a layer comprising the chemically amplified positive photoresist composition of the invention; and protective films formed on both sides of the layer. The layer comprising the chemically amplified positive photoresist composition may generally have a thickness in the range of 10 to 150 μm, preferably 20 to 120 μm, more preferably 20 to 80 μm. The protective films are not particularly restricted, and resin films that have been used in conventional dry films may be used. In one case, one may be a polyethylene terephthalate film, and the other may be one selected from the group consisting of a polyethylene terephthalate film, a polypropylene film, and a polyethylene film.

For example, the chemically amplified positive dry film as described above may be produced as described below. Specifically, a solution of the chemically amplified positive photoresist composition prepared as described above is applied to one of the protective films, and the solvent is removed by heating, so that a desired coating film is formed. The drying conditions may be generally 60 to 100° C. and about 5 to 20 minutes, although they depend on the type or formulation rate of each ingredient in the composition, the thickness of the coating film, or the like.

A process of forming a resist pattern using the chemically amplified dry film obtained as described above may include stripping off one of the protective films from the chemically amplified positive dry film, laminating the resulting film on a support in such a manner that the exposed surface faces the above support side, so that a photoresist layer is obtained, then performing prebaking to dry the resist, and then stripping off the other protective film.

The resulting photoresist layer provided on the support in such a manner may be subjected to the same process as described above for the photoresist layer formed by direct application to the support so that a resist pattern can be formed.

The chemically amplified negative photoresist composition of the invention contains an ingredient (E) comprising the photo-acid generator of the invention, which is a compound generating an acid when irradiated with light or a radiation; an alkali-soluble resin (F) having a phenolic hydroxyl group; and a crosslinking agent (G).

Alkali-Soluble Resin (F) Having Phenolic Hydroxyl Group

In the invention, examples of the “alkali-soluble resin having a phenolic hydroxyl group” (hereinafter referred to as “phenolic resin (F)”), which may be used, include a novolac resin, polyhydroxystyrene, a polyhydroxystyrene copolymer, a copolymer of hydroxystyrene and styrene, a copolymer of hydroxystyrene, styrene, and a (meth)acrylic acid derivative, a phenol-xylylene glycol condensate resin, a cresol-xylylene glycol condensate resin, and a phenol-dicyclopentadiene condensate resin. Among them, preferred are a novolac resin, polyhydroxystyrene, a polyhydroxystyrene copolymer, a copolymer of hydroxystyrene and styrene, a copolymer of hydroxystyrene, styrene, and a (meth)acrylic acid derivative, and a phenol-xylylene glycol condensate resin. These phenolic resins (F) may be used alone or in a mixture of two or more.

The phenolic resin (F) may also contain a low-molecular-weight phenolic compound as a partial component.

Examples of the above low-molecular-weight phenolic compound include 4,4′-dihydroxydiphenylmethane and 4,4′-dihydroxydiphenyl ether.

Crosslinking Agent (G)

In the invention, the “crosslinking agent” (hereinafter also referred to as “crosslinking agent (G)”) is not particularly limited as long as it acts as a crosslinking component (curing component) reactive with the aforesaid phenolic resin (F). Examples of the above crosslinking agent (G) include a compound having at least two alkyl-etherified amino groups in the molecule, a compound having at least two alkyl-etherified benzene skeletons in the molecule, an oxirane ring-containing compound, a thiirane ring-containing compound, an oxetanyl group-containing compound, and an isocyanate group-containing compound (including a blocked derivative).

Among these crosslinking agents (G), preferred are a compound having at least two alkyl-etherified amino groups in the molecule or an oxirane ring-containing compound. More preferably, a compound having at least two alkyl-etherified amino groups in the molecule is used in combination with an oxirane ring-containing compound.

In the invention, the amount of the crosslinking agent (G) formulated is preferably from 1 to 100 parts by weight, more preferably from 5 to 50 parts by weight, based on 100 parts by weight of the aforesaid phenolic resin (F). When the amount of the crosslinking agent (G) formulated is from 1 to 100 parts by weight, the curing reaction can sufficiently proceed, so that the resulting cured product can have a good pattern shape with a high resolution and have excellent heat resistance and electric insulation, which is preferred.

When a compound having alkyl-etherified amino groups is used in combination with an oxirane ring-containing compound, the content rate of the oxirane ring-containing compound is preferably 50% by weight or less, more preferably from 5 to 40% by weight, in particular, preferably from 5 to 30% by weight, based on the total amount of the compound having alkyl-etherified amino groups and the oxirane ring-containing compound, which is normalized as 100% by weight.

In this case, the resulting cured film also has excellent chemical resistance without losing the high resolution, which is preferred.

Cross-Linked Fine Particles (H)

The chemically amplified negative photoresist composition of the invention may further contain crosslinked fine particles (hereinafter also referred to as “crosslinked fine particles (H)”) for improving the durability and thermal shock resistance of the resulting cured product.

The average particle size of the crosslinked fine particles (H) is generally from 30 to 500 nm, preferably from 40 to 200 nm, more preferably from 50 to 120 nm.

A method of controlling the particle size of the crosslinked fine particles (H) is not particularly limited. For example, when the crosslinked fine particles are synthesized by emulsion polymerization, the number of micelles during the emulsion polymerization may be controlled by the amount of the emulsifying agent used so that the particle size can be controlled.

The average particle size of the crosslinked fine particles (H) is a value obtained by a process that includes diluting a dispersion of the crosslinked fine particles by a conventional method and measuring the dilution with a light scattering particle size analyzer or the like.

The amount of the crosslinked fine particles (H) formulated is preferably from 0.5 to 50 parts by weight, more preferably from 1 to 30 parts by weight, based on 100 parts by weight of the aforesaid phenolic resin (F). When the amount of the crosslinked fine particles (H) is from 0.5 to 50 parts by weight, they have excellent compatibility with other ingredients or excellent dispersibility, so that the resulting cured film can have improved thermal shock resistance and heat resistance.

Adhesion Auxiliary Agent

The chemically amplified negative photoresist composition of the invention may also contain an adhesion auxiliary agent for improving adhesion to the base material.

Examples of the above adhesion auxiliary agent include functional silane coupling agents having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group.

The amount of the adhesion auxiliary agent formulated is preferably from 0.2 to 10 parts by weight, more preferably from 0.5 to 8 parts by weight, based on 100 parts by weight of the aforesaid phenolic resin (F). When the amount of the adhesion auxiliary agent formulated is from 0.2 to 10 parts by weight, excellent storage stability and good adhesion can be achieved, which is preferred.

Solvent

The chemically amplified negative photoresist composition of the invention may also contain a solvent for improving the handleability of the resin composition or controlling viscosity or storage stability.

Specific examples of the above solvent include, but are not particularly limited to, those listed above.

Other Additives

If necessary, the chemically amplified negative photoresist composition of the invention may also contain an additional additive in such an extent that the characteristics of the invention are not impaired. Examples of such an additional additive include an inorganic filler, a sensitizer, a quencher, a leveling agent, and a surfactant.

A method for preparing the chemically amplified negative photoresist composition of the invention is not particularly limited, and it may be prepared by any known method. The composition may also be prepared by placing each ingredient in a sample vial, completely sealing the vial with a plug, and stirring the ingredients on a wave rotor.

The cured product of the invention comprises a product obtained by curing the aforesaid chemically amplified negative photoresist composition.

The chemically amplified negative photoresist composition of the invention described above has high remaining thickness ratio and excellent resolution, and the cured product has excellent electric insulation, thermal shock resistance and the like. Therefore, the cured product is suitable for use as a surface protecting film, a planarizing film, an interlayer dielectric film material, or the like in electronic components such as semiconductor devices and semiconductor packages.

To form the cured product of the invention, the chemically amplified negative photoresist composition of the invention as described above is first applied to a support (such as a resin-bearing copper foil, a copper-clad laminate, a silicon wafer having a sputtered metal film, or an alumina substrate), and the solvent and the like are evaporated by drying, so that a coating film is formed. Subsequently, the coating film is exposed to light through a desired mask pattern and heat-treated (hereinafter the heat treatment is referred to as “PEB”) so that the reaction between the phenolic resin (F) and the crosslinking agent (G) is accelerated. The unexposed part is then dissolved and removed by development with an alkaline developing solution, so that a desired pattern is obtained. Heat treatment for producing insulating film characteristics is further performed, so that a cured film is obtained.

An application method such as dipping, spraying, bar coating, roller coating, or spin coating may be used to apply the resin composition to the support. The thickness of the coating film can be appropriately controlled by controlling application means or the solids content or viscosity of a solution of the composition.

Examples of radiations for use in the exposure include ultraviolet rays from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, g-line steppers, h-line steppers, i-line steppers, gh-line steppers, or ghi-line steppers, electron beams, and laser beams. The exposure dose is appropriately selected depending on the light source used, the thickness of the resin film, or the like. For example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, the exposure dose may be from about 100 to 50,000 J/m² for a resin film thickness of 1 to 50 μm.

After the exposure, the above PEB treatment is performed to accelerate the curing reaction between the phenolic resin (F) and the crosslinking agent (G), which is induced by the generated acid. The PEB conditions are generally 70 to 150° C., preferably 80 to 120° C., and about 1 to 60 minutes, although they depend on the amount of the resin composition formulated, the thickness of the film used, or the like. Subsequently, the unexposed part is dissolved and removed by development with an alkaline developing solution, so that a desired pattern is formed. In this case, the development method may be a shower development method, a spray development method, an immersion development method, a puddle development method, or the like. The development conditions are generally 20 to 40° C. and about 1 to 20 minutes.

After the development, the film may be sufficiently cured by heat treatment so that insulting film characteristics can be sufficiently exerted. The curing conditions are not restricted. Depending on the intended use of the cured product, the composition may be cured by heating at a temperature of 50 to 250° C. for about 30 minutes to 10 hours. Two-stage heating may also be performed so that the curing can sufficiently proceed or deformation of the resulting pattern shape can be prevented. For example, the curing at the first stage may be performed by heating at a temperature of 50 to 120° C. for about 5 minutes to 2 hours, and the curing at the second state may be performed at a temperature of 80 to 250° C. for about 10 minutes to 10 hours. Under such curing conditions, a general oven, an infrared furnace, or the like can be used as the heating equipment.

EXAMPLES

Hereinafter, the invention is more specifically described with reference to Examples, which however are not intended to limit the invention. Hereinafter, “parts” means parts by weight, and “%” means % by weight, unless otherwise specified.

Production Example 1 Synthesis of 4-(phenylthio)biphenyl

Uniformly mixed were 3.0 parts of 4-bromobiphenyl, 1.7 parts of thiophenol, 2.5 parts of sodium tert-butoxide, 0.15 parts of tetrakis(triphenylphosphine)palladium, and 64.3 parts of 1-butanol, and allowed to react at 120° C. for 2 hours. The reaction solution was cooled to room temperature (about 25° C.) and then filtered. The filtrate was transferred to a rotary evaporator, and the solvent was removed by distillation, so that a red-brown, crystalline product was obtained. The product was dissolved in 70 parts of dichloromethane, and 50 parts of an aqueous saturated sodium hydrogen carbonate solution was added thereto. After washing three times by liquid-liquid separation, the dichloromethane layer was washed with 70 parts of distilled water until the pH became neutral. The dichloromethane layer was transferred to a rotary evaporator, and the solvent was removed by distillation, so that a brown, crystalline product was obtained. Twenty parts of hexane was added thereto, and the product was dispersed in hexane using an ultrasonic cleaner. The operation of standing for about 15 minutes and then removing the supernatant was repeated three times to wash the resulting solid, and the solvent was removed with a rotary evaporator, so that brown crystalline 4-(phenylthio)biphenyl was obtained in a yield of 84%. The product was identified by ¹H-NMR {d6-dimethylsulfoxide, δ (ppm) 7.6-7.7 (4H, m), 7.3-7.5 (10H, m)}.

Production Example 2 Synthesis of a Mixture Containing 4-[(phenyl)sulfinyl]biphenyl and 4-(phenylthio)biphenyl

Uniformly mixed were 2.0 parts of 4-(phenylthio) biphenyl synthesized in Production Example 1, 8.0 parts of acetonitrile, 0.037 parts of sulfuric acid, and 0.43 parts of an aqueous 30% hydrogen peroxide solution, and allowed to react at 65° C. for 3 hours. After the reaction solution was cooled to room temperature (about 25° C.), 30 parts of dichloromethane was added, and washing by liquid-liquid separation was performed with 40 parts of distilled water until the pH became neutral. The dichloromethane layer was transferred to a rotary evaporator, and the solvent was removed by distillation, so that a brown liquid mixture containing 55% of 4-[(phenyl)sulfinyl]biphenyl and 45% of 4-(phenylthio)biphenyl. The product was isolated by column chromatography (eluent: ethyl acetate/hexane=1/1 in volume ratio) and then identified by ¹H-NMR. The ¹H-NMR data for 4-[(phenyl)sulfinyl]biphenyl: {d6-dimethylsulfoxide, δ (ppm) 7.7-7.9 (4H, m), 7.3-7.6 (10H, m)}. The content was calculated from the peak area ratio obtained by HPLC analysis of the mixture.

Production Example 3 Synthesis of 4-[(2-methylphenyl)thio]biphenyl

Brown crystalline 4-[(2-methylphenyl)thio]biphenyl was obtained in a yield of 89% as in Production Example 1, except that “1.7 parts of thiophenol” was replaced with “1.8 parts of 2-methylthiophenol”. The product was identified by ¹H-NMR {d6-dimethylsulfoxide, δ (ppm) 7.6-7.7 (4H, m), 7.3-7.5 (9H, m), 2.3 (3H, s)}.

Production Example 4 Synthesis of a Mixture Containing 4-[(2-methylphenyl)sulfinyl]biphenyl and 4-[(2-methylphenyl)thio]biphenyl

A brown liquid mixture containing 51% of 4-[(2-methylphenyl)sulfinyl]biphenyl and 49% of 4-[(2-methylphenyl)thio]biphenyl was obtained as in Production Example 2, except that “2.0 parts of 4-(phenylthio)biphenyl” was replaced with “2.1 parts of 4-[(2-methylphenyl)thio]biphenyl” synthesized in Production Example 3. The product was isolated by column chromatography (eluent: ethyl acetate/hexane=1/1 in volume ratio) and then identified by ¹H-NMR. The ¹H-NMR data for 4-[(2-methylphenyl)sulfinyl]biphenyl: {d6-dimethylsulfoxide, δ (ppm) 7.6-8.0 (7H, m), 7.1-7.6 (6H, m), 2.3-2.4 (3H, s)}. The content was calculated from the peak area ratio obtained by HPLC analysis of the mixture.

Production Example 5 Synthesis of 4-[(2-methoxyphenyl)thio]biphenyl

Brown crystalline 4-[(2-methoxyphenyl)thio]biphenyl was obtained in a yield of 85% as in Production Example 1, except that “1.7 parts of thiophenol” was replaced with “2.2 parts of 2-methoxythiophenol”. The product was identified by ¹H-NMR {d6-dimethylsulfoxide, δ (ppm) 7.6-7.7 (4H, m), 7.3-7.5 (9H, m), 3.7 (3H, s)}.

Production Example 6 Synthesis of a Mixture Containing 4-[(2-methoxyphenyl)sulfinyl]biphenyl and 4-[(2-methoxyphenyl)thio]biphenyl

A brown liquid mixture containing 51% of 4-[(2-methoxyphenyl)sulfinyl]biphenyl and 49% of 4-[(2-methoxyphenyl)thio]biphenyl was obtained as in Production Example 2, except that “2.0 parts of 4-(phenylthio)biphenyl” was replaced with “2.2 parts of 4-[(2-methoxyphenyl)thio]biphenyl” synthesized in Production Example 5. The product was isolated by column chromatography (eluent: ethyl acetate/hexane=1/1 in volume ratio) and then identified by ¹H-NMR. The H-NMR data for 4-[(2-methoxyphenyl)sulfinyl]biphenyl: {d6-dimethylsulfoxide, δ (ppm) 7.6-8.0 (7H, m), 7.1-7.6 (6H, m), 3.6-3.7 (3H, s)}. The content was calculated from the peak area ratio obtained by HPLC analysis of the mixture.

Production Example 7 Synthesis of 2-(phenylthio) thioxanthone

Uniformly mixed were 11.0 parts of 2-chlorothioxanthone, 4.9 parts of thiophenol, 2.5 parts of potassium hydroxide, 162 parts of N,N-dimethylformamide, and allowed to react at 130° C. for 9 hours. Subsequently, the reaction solution was cooled to room temperature (about 25° C.) and poured into 200 parts of distilled water, so that the product was precipitated. The product was filtered, and the residue was washed with water until the pH of the filtrate became neutral. Subsequently, the residue was dried under reduced pressure, so that a yellow powdery product was obtained. The product was purified by column chromatography (eluent: toluene/hexane=1/1 in volume ratio) to give 2-(phenylthio)thioxanthone in a yield of 45%. The product was identified by ¹H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.43 (1H, d), 8.25 (1H, s), 7.75-7.90 (3H, m), 7.66 (1H, d), 7.60 (1H, t), 7.42-7.46 (5H, m)}.

Example 1 Synthesis of [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tris(pentafluoroethyl)trifluorophosphate (3)

Uniformly mixed were 2.0 parts of the mixture synthesized in Production Example 2 containing 55% of 4-[(phenyl)sulfinyl]biphenyl and 45% of 4-(phenylthio)biphenyl, 0.24 parts of 4-(phenylthio)biphenyl synthesized in Production Example 1, 1.2 parts of acetic anhydride, 0.72 parts of trifluoromethanesulfonic acid, and 6.5 parts of acetonitrile, and allowed to react at 60° C. for 2 hours. The reaction solution was cooled to room temperature (about 25° C.) and poured into 30 parts of distilled water. The mixture was extracted with 30 parts of dichloromethane, and the dichloromethane layer was washed with water until the pH of the water layer became neutral. The dichloromethane layer was transferred to a rotary evaporator, and the solvent was removed by distillation, so that a brown liquid product was obtained. Thereto was added 10 parts of ethyl acetate, and the product was dissolved in a water bath at 60° C. Subsequently, after 30 parts of hexane was added and stirred, the operation of allowing the mixture to stand for 30 minutes in a refrigerator (about 5° C.) and then removing the supernatant was performed twice to wash the product. The product was transferred to a rotary evaporator, and the solvent was removed by distillation, so that [4-(4-biphenylylthio) phenyl]-4-biphenylylphenylsulfonium triflate (triflate=trifluoromethanesulfonate anion) was obtained.

(Metathesis Process)

The triflate was dissolved in 27 parts of dichloromethane, and the solution was poured into 21 parts of an aqueous solution of 10% potassium tris(pentafluoroethyl)trifluorophosphate. Subsequently, the mixture was stirred at room temperature (about 25° C.) for 3 hours. After the dichloromethane layer was washed three times with water by liquid-liquid separation, it was transferred to a rotary evaporator, and the solvent was removed by distillation, so that [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tris(pentafluoroethyl)trifluorophosphate was obtained in a yield of 88%. The product was identified by ¹H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (17H, m), 7.3-7.6 (8H, m)}. The absorption of the P—F bond was observed at about 840 cm⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

Example 2 Synthesis of [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium hexafluoroantimonate (4)

[4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium hexafluoroantimonate was obtained in a yield of 85% as in Example 1, except that “21 parts of an aqueous solution of 10% potassium tris(pentafluoroethyl)trifluorophosphate” was replaced with “24 parts of 5% potassium hexafluoroantimonate”. The product was identified by ¹H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (17H, m), 7.3-7.6 (8H, m)}. The absorption of the Sb—F bond was observed at about 650 cm⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

Example 3 Synthesis of [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tetrakis(pentafluorophenyl)borate (5)

[4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tetrakis(pentafluorophenyl)borate was obtained in a yield of 90% as in Example 1, except that “21 parts of an aqueous solution of 10% potassium tris(pentafluoroethyl)trifluorophosphate” was replaced with “30 parts of 10% lithium tetrakis(pentafluorophenyl)borate”. The product was identified by ¹H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (17H, m), 7.3-7.6 (8H, m)}. The absorption of the B—C bond was observed at about 980 cm⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

Example 4 Synthesis of [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium hexafluorophosphate (6)

[4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium hexafluorophosphate was obtained in a yield of 89% as in Example 1, except that “21 parts of an aqueous solution of 10% potassium tris(pentafluoroethyl)trifluorophosphate” was replaced with “16 parts of 5% potassium hexafluorophosphate”. The product was identified by ¹H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (17H, m), 7.3-7.6 (8H, m)}. The absorption of the P—F bond was observed at about 540 cm⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

Example 5 Synthesis of [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium nonafluorobutanesulfonate (7)

[4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium nonafluorobutanesulfonate was obtained in a yield of 87% as in Example 1, except that “0.72 parts of trifluoromethanesulfonic acid” was replaced with “1.42 parts of nonafluorobutanesulfonic acid” and that metathesis was not performed. The product was identified by ¹H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (17H, m), 7.3-7.6 (8H, m)}. The absorption of the C—F bond was observed at about 1,200 cm⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

Example 6 Synthesis of [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium bis(trifluoromethanesulfonyl)imide (8)

[4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium bis(trifluoromethanesulfonyl) imide was obtained in a yield of 85% as in Example 1, except that “21 parts of an aqueous solution of 10% potassium tris(pentafluoroethyl)trifluorophosphate” was replaced with “14 parts of 10% lithium bis(trifluoromethanesulfonyl) imide” The product was identified by ¹H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (17H, m), 7.3-7.6 (8H, m)}. The absorption of the C—F bond was observed at about 1,200 cm⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

Example 7 Synthesis of [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tris(trifluoromethanesulfonyl)methide (9)

[4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tris(trifluoromethanesulfonyl)methide was obtained in a yield of 86% as in Example 1, except that “21 parts of an aqueous solution of 10% potassium tris(pentafluoroethyl)trifluorophosphate” was replaced with “20 parts of 10% lithium tris(trifluoromethanesulfonyl)methide”. The product was identified by ¹H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (17H, m), 7.3-7.6 (8H, m)}. The absorption of the C—F bond was observed at about 1,200 cm⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

Example 8 Synthesis of [4-(4-biphenylylthio) phenyl]-4-biphenylylphenylsulfonium methanesulfonate (10)

[4-(4-biphenylylthio) phenyl]-4-biphenylylphenylsulfonium methanesulfonate was obtained in a yield of 65% as in Example 1, except that “0.72 parts of trifluoromethanesulfonic acid” was replaced with “2.28 parts of methanesulfonic acid” and that metathesis was not performed. The product was identified by ¹H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (17H, m), 7.3-7.6 (8H, m), 2.7 (3H, s)}.

Example 9 Synthesis of (2-methyl)phenyl[4-(4-biphenylylthio)-3-methylphenyl]-4-biphenylylsulfonium tris(pentafluoroethyl)trifluorophosphate (11)

Uniformly mixed were 2.0 parts of the mixture synthesized in Production Example 4 containing 51% of 4-[(2-methylphenyl) sulfinyl]biphenyl and 49% of 4-[(2-methylphenyl)thio]biphenyl, 0.08 parts of 4-[(2-methylphenyl)thio]biphenyl synthesized in Production Example 3, 1.1 parts of acetic anhydride, 0.65 parts of trifluoromethanesulfonic acid, and 7.7 parts of acetonitrile, and allowed to react at 60° C. for 2 hours. The reaction solution was cooled to room temperature (about 25° C.) and poured into 30 parts of distilled water. The mixture was extracted with 30 parts of dichloromethane, and the dichloromethane layer was washed with water until the pH of the water layer became neutral. The dichloromethane layer was transferred to a rotary evaporator, and the solvent was removed by distillation, so that a brown liquid product was obtained. Thereto was added 10 parts of ethyl acetate, and the product was dissolved in a water bath at 60° C. Subsequently, after 30 parts of hexane was added and stirred, the operation of allowing the mixture to stand for 30 minutes in a refrigerator (about 5° C.) and then removing the supernatant was performed twice to wash the product. The product was transferred to a rotary evaporator, and the solvent was removed by distillation, so that (2-methyl)phenyl [4-(4-biphenylylthio)-3-methylphenyl]-4-biphenylylsulfonium triflate (triflate=trifluoromethanesulfonate anion) was obtained.

(Metathesis Process)

The triflate was dissolved in 25 parts of dichloromethane, and the solution was poured into 21 parts of an aqueous solution of 10% potassium tris(pentafluoroethyl)trifluorophosphate. Subsequently, the mixture was stirred at room temperature (about 25° C.) for 3 hours. After the dichloromethane layer was washed three times with water by liquid-liquid separation, it was transferred to a rotary evaporator, and the solvent was removed by distillation, so that (2-methyl)phenyl [4-(4-biphenylylthio)-3-methylphenyl]-4-biphenylylsulfonium tris(pentafluoroethyl)trifluorophosphate was obtained in a yield of 92%. The product was identified by ¹H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (15H, m), 7.3-7.6 (8H, m), 2.5 (6H, s)}. The absorption of the P—F bond was observed at about 840 cm⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

Example 10 Synthesis of (2-methyl)phenyl [4-(4-biphenylylthio)-3-methylphenyl]-4-biphenylylsulfonium hexafluoroantimonate (12) (2-methyl)phenyl

[4-(4-biphenylylthio)-3-methylphenyl]-4-biphenylylsulfonium hexafluoroantimonate was obtained in a yield of 85% as in Example 9, except that “21 parts of an aqueous solution of 10% potassium tris(pentafluoroethyl)trifluorophosphate” was replaced with “22 parts of 5% potassium hexafluoroantimonate”. The product was identified by ¹H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (15H, m), 7.3-7.6 (8H, m), 2.5 (6H, s)}. The absorption of the Sb—F bond was observed at about 650 cm⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

Example 11 Synthesis of (2-methyl)phenyl [4-(4-biphenylylthio)-3-methylphenyl]-4-biphenylylsulfonium tetrakis(pentafluorophenyl)borate (13) (2-methyl)phenyl

[4-(4-biphenylylthio)-3-methylphenyl]-4-biphenylylsulfonium tetrakis(pentafluorophenyl)borate was obtained in a yield of 92% as in Example 9, except that “21 parts of an aqueous solution of 10% potassium tris(pentafluoroethyl)trifluorophosphate” was replaced with “27 parts of 10% lithium tetrakis(pentafluorophenyl)borate”. The product was identified by ¹H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (15H, m), 7.3-7.6 (8H, m), 2.5 (6H, s)}. The absorption of the B—C bond was observed at about 980 cm⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

Example 12 Synthesis of (2-methyl)phenyl [4-(4-biphenylylthio)-3-methylphenyl]-4-biphenylylsulfonium hexafluorophosphate (14) (2-methyl)phenyl

[4-(4-biphenylylthio)-3-methylphenyl]-4-biphenylylsulfonium hexafluorophosphate was obtained in a yield of 90% as in Example 9, except that “21 parts of an aqueous solution of 10% potassium tris(pentafluoroethyl)trifluorophosphate” was replaced with “15 parts of 5% potassium hexafluorophosphate”. The product was identified by ¹H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (15H, m), 7.3-7.6 (8H, m), 2.5 (6H, s)}. The absorption of the P—F bond was observed at about 540 cm⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

Example 13 Synthesis of (2-methoxy)phenyl [4-(4-biphenylylthio)-3-methoxyphenyl]-4-biphenylylsulfonium tris(pentafluoroethyl)trifluorophosphate (15)

Uniformly mixed were 2.0 parts of the mixture synthesized in Production Example 6 containing 51% of 4-[(2-methoxyphenyl) sulfinyl]biphenyl and 49% of 4-[(2-methoxyphenyl)thio]biphenyl, 0.08 parts of 4-[(2-methoxyphenyl)thio]biphenyl synthesized in Production Example 5, 1.0 part of acetic anhydride, 0.6 parts of trifluoromethanesulfonic acid, and 7.7 parts of acetonitrile, and allowed to react at 60° C. for 2 hours. The reaction solution was cooled to room temperature (about 25° C.) and poured into 30 parts of distilled water. The mixture was extracted with 30 parts of dichloromethane, and the dichloromethane layer was washed with water until the pH of the water layer became neutral. The dichloromethane layer was transferred to a rotary evaporator, and the solvent was removed by distillation, so that a brown liquid product was obtained. Thereto was added 10 parts of ethyl acetate, and the product was dissolved in a water bath at 60° C. Subsequently, after 30 parts of hexane was added and stirred, the operation of allowing the mixture to stand for 30 minutes in a refrigerator (about 5° C.) and then removing the supernatant was performed twice to wash the product. The product was transferred to a rotary evaporator, and the solvent was removed by distillation, so that (2-methyl) phenyl [4-(4-biphenylylthio)-3-methoxyphenyl]4-biphenylylsulfonium triflate (triflate=trifluoromethanesulfonate anion) was obtained.

(Metathesis Process)

The triflate was dissolved in 25 parts of dichloromethane, and the solution was poured into 19 parts of an aqueous solution of 10% potassium tris(pentafluoroethyl)trifluorophosphate. Subsequently, the mixture was stirred at room temperature (about 25° C.) for 3 hours. After the dichloromethane layer was washed three times with water by liquid-liquid separation, it was transferred to a rotary evaporator, and the solvent was removed by distillation, so that (2-methoxy)phenyl [4-(4-biphenylylthio)-3-methoxyphenyl]4-biphenylylsulfonium tris(pentafluoroethyl)trifluorophosphate was obtained in a yield of 90%. The product was identified by ¹H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (15H, m), 7.3-7.6 (8H, m), 3.6-3.8 (6H, s)}. The absorption of the P—F bond was observed at about 840 cm⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

[Production of Sulfonium Salt Mixture] Production Example 8 Production-1 of a Mixture of 4-(phenylthio)biphenyl and [4-(phenyl)sulfinyl]biphenyl

After 10.0 parts of 4-(phenylthio)biphenyl, 40.0 parts of acetonitrile, and 0.19 parts of sulfuric acid were added and uniformly mixed, the mixture was heated to 50° C., and 2.59 parts of an aqueous 30% hydrogen peroxide solution was added dropwise thereto over 10 minutes. Subsequently, the mixture was allowed to react at 65° C. for 3 hours. After the reaction solution was cooled to room temperature (about 25° C.), 150 parts of dichloromethane was added, and the dichloromethane layer was washed with 200 parts of distilled water until the pH became neutral. The dichloromethane layer was transferred to a rotary evaporator, and the solvent was removed by distillation, so that 9.8 parts of a brown liquid mixture containing 39% of 4-(phenylthio)biphenyl and 61% of [4-(phenyl)sulfinyl]biphenyl was obtained. The content was calculated from the peak area ratio obtained by HPLC analysis of the mixture.

Production Example 9 Production-2 of a Mixture of 4-(phenylthio)biphenyl and [4-(phenyl)sulfinyl]biphenyl

A brown liquid mixture containing 37% of 4-(phenylthio)biphenyl and 63% of [4-(phenyl)sulfinyl]biphenyl was obtained in an amount of 9.9 parts as in Production Example 8, except that the amount of the aqueous 30% hydrogen peroxide solution was changed from 2.59 parts to 2.66 parts.

Production Example 10 Production-3 of a Mixture of 4-(phenylthio)biphenyl and [4-(phenyl)sulfinyl]biphenyl

A brown liquid mixture containing 42% of 4-(phenylthio)biphenyl and 58% of [4-(phenyl)sulfinyl]biphenyl was obtained in an amount of 9.8 parts as in Production Example 8, except that the amount of the aqueous 30% hydrogen peroxide solution was changed from 2.59 parts to 2.44 parts.

Production Example 11 Production-4 of a Mixture of 4-(phenylthio)biphenyl and [4-(phenyl)sulfinyl]biphenyl

A brown liquid mixture containing 46% of 4-(phenylthio)biphenyl and 54% of [4-(phenyl)sulfinyl]biphenyl was obtained in an amount of 9.8 parts as in Production Example 8, except that the amount of the aqueous 30% hydrogen peroxide solution was changed from 2.59 parts to 2.27 parts.

Production Example 12 Production-5 of a Mixture of 4-(phenylthio)biphenyl and [4-(phenyl)sulfinyl]biphenyl

A brown liquid mixture containing 48.3% of 4-(phenylthio)biphenyl and 51.7% of [4-(phenyl)sulfinyl]biphenyl was obtained in an amount of 9.8 parts as in Production Example 8, except that the amount of the aqueous 30% hydrogen peroxide solution was changed from 2.59 parts to 2.17 parts.

Production Example 13 Production of a Mixture of 4-[(2-methylphenyl)thio]biphenyl and 4-[(2-methylphenyl)sulfinyl]biphenyl

A brown liquid mixture containing 42% of 4-[(2-methylphenyl)thio]biphenyl and 58% of 4-[(2-methylphenyl)sulfinyl]biphenyl was obtained in an amount of 10.3 parts as in Production Example 8, except that 10.0 parts of 4-(phenylthio)biphenyl was replaced with 10.5 parts of 4-[(2-methylphenyl)thio]biphenyl and that the amount of the aqueous 30% hydrogen peroxide solution was changed from 2.59 parts to 2.44 parts. The content of each compound was calculated from the peak area ratio obtained by HPLC analysis of the mixture.

Production Example 14 Production of a Mixture of 4-[(2-methoxyphenyl)thio]biphenyl and 4-[(2-methoxyphenyl)sulfinyl]biphenyl

A brown liquid mixture containing 42% of 4-[(2-methoxyphenyl)thio]biphenyl and 58% of 4-[(2-methoxyphenyl)sulfinyl]biphenyl was obtained in an amount of 10.9 parts as in Production Example 8, except that 10.0 parts of 4-(phenylthio)biphenyl was replaced with 11.1 parts of 4-[(2-methoxyphenyl)thio]biphenyl and that the amount of the aqueous 30% hydrogen peroxide solution was changed from 2.59 parts to 2.44 parts. The content of each compound was calculated from the peak area ratio obtained by HPLC analysis of the mixture.

Example 14 Production-1 of a Mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium tris(pentafluoroethyl)trifluorophosphate [compound (a)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis[tris(pentafluoroethyl)trifluorophosphate] [compound (b)]

In 15.5 parts of methanesulfonic acid was dissolved 4.1 parts of the mixture produced in Production Example 8 [ a mixture containing 39% of 4-(phenylthio)biphenyl and 61% of [4-(phenyl)sulfinyl]biphenyl], and 2.8 parts of acetic anhydride was added dropwise thereto at room temperature. Subsequently, the mixture was allowed to react at 60° C. for 6 hours. The reaction liquid was cooled to room temperature (about 25° C.) and then poured into 200 parts of distilled water.

Under stirring, 52.7 parts of an aqueous solution of 10% potassium tris(pentafluoroethyl)trifluorophosphate was added dropwise thereto. After continuous stirring at room temperature (about 25° C.) for 3 hours, 80 parts of dichloromethane was added, and the target product was extracted. The organic layer (dichloromethane layer) was separated and then washed five times with water. After the organic layer was transferred to a rotary evaporator, the solvent was removed by distillation, and then the residue was washed with a toluene/hexane solution, so that 6.8 parts of a mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium tris(pentafluoroethyl)trifluorophosphate [compound (a)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis[tris(pentafluoroethyl)trifluorophosphate] [compound (b)] was obtained [the molar ratios of compounds (a) and (b) were 50% by mole and 50% by mole, respectively]. The product was identified by ¹H-NMR, infrared absorption spectroscopic analysis (IR), and LC-MS. {¹H-NMR: d6-dimethylsulfoxide; δ (ppm) 7.7-8.2 (m), 7.3-7.6 (m); IR (KBr tablet method): C—F bond characteristic absorption; about 1,200 cm⁻¹; LC-MS: molecular ion peak of compound (a); 524, molecular ion peak of compound (b); 393}. The mixture ratio (% by mole) was calculated from the peak area ratio obtained by HPLC analysis.

Example 15 Production-2 of a Mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium tris(pentafluoroethyl)trifluorophosphate [compound (a)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis[tris(pentafluoroethyl)trifluorophosphate] [compound (b)]

A mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium tris(pentafluoroethyl)trifluorophosphate [compound (a)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis[tris(pentafluoroethyl)trifluorophosphate] [compound (b)] was obtained in an amount of 6.7 parts [the molar ratios of compounds (a) and (b) were 40% by mole and 60% by mole, respectively] as in Example 14, except that 4.1 parts of the “mixture containing 39% of 4-(phenylthio)biphenyl and 61% of [4-(phenyl)sulfinyl]biphenyl” produced in Production Example 8 was replaced with 4.0 parts of the “mixture containing 37% of 4-(phenylthio)biphenyl and 63% of [4-(phenyl)sulfinyl]biphenyl” produced in Production Example 9.

Example 16 Production-3 of a Mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium tris(pentafluoroethyl)trifluorophosphate [compound (a)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis[tris(pentafluoroethyl)trifluorophosphate] [compound (b)]

A mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium tris(pentafluoroethyl)trifluorophosphate [compound (a)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis[tris(pentafluoroethyl)trifluorophosphate] [compound (b)] was obtained in an amount of 7.0 parts [the molar ratios of compounds (a) and (b) were 70% by mole and 30% by mole, respectively] as in Example 14, except that 4.1 parts of the “mixture containing 39% of 4-(phenylthio)biphenyl and 61% of [4-(phenyl)sulfinyl]biphenyl” produced in Production Example 8 was replaced with 4.4 parts of the “mixture containing 42% of 4-(phenylthio)biphenyl and 58% of [4-(phenyl)sulfinyl]biphenyl” produced in Production Example 10.

Example 17 Production-4 of a Mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium tris(pentafluoroethyl)trifluorophosphate [compound (a)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis[tris(pentafluoroethyl)trifluorophosphate] [compound (b)]

A mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium tris(pentafluoroethyl)trifluorophosphate [compound (a)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis[tris(pentafluoroethyl)trifluorophosphate] [compound (b)] was obtained in an amount of 7.3 parts [the molar ratios of compounds (a) and (b) were 90% by mole and 10% by mole, respectively] as in Example 14, except that 4.1 parts of the “mixture containing 39% of 4-(phenylthio)biphenyl and 61% of [4-(phenyl)sulfinyl]biphenyl” produced in Production Example 8 was replaced with 4.7 parts of the “mixture containing 46% of 4-(phenylthio)biphenyl and 54% of [4-(phenyl)sulfinyl]biphenyl” produced in Production Example 11.

Example 18 Production-5 of a Mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium tris(pentafluoroethyl)trifluorophosphate [compound (a)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis[tris(pentafluoroethyl)trifluorophosphate] [compound (b)]

A mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium tris(pentafluoroethyl)trifluorophosphate [compound (a)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis[tris(pentafluoroethyl)trifluorophosphate] [compound (b)] was obtained in an amount of 7.4 parts [the molar ratios of compounds (a) and (b) were 99% by mole and 1% by mole, respectively] as in Example 14, except that 4.1 parts of the “mixture containing 39% of 4-(phenylthio)biphenyl and 61% of [4-(phenyl)sulfinyl]biphenyl” produced in Production Example 8 was replaced with 4.9 parts of the “mixture containing 48.3% of 4-(phenylthio)biphenyl and 51.7% of [4-(phenyl)sulfinyl]biphenyl” produced in Production Example 12.

Example 19 Production-1 of a Mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium tetrakis(pentafluorophenyl)borate [compound (c)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis[tetrakis(pentafluorophenyl)borate] [compound (d)]

A mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium tetrakis(pentafluorophenyl)borate [compound (c)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis[tetrakis(pentafluorophenyl)borate] [compound (d)] was obtained in an amount of 6.8 parts [the molar ratios of compounds (c) and (d) were 50% by mole and 50% by mole, respectively] as in Example 14, except that “52.7 parts of an aqueous solution of 10% potassium tris(pentafluoroethyl)trifluorophosphate” was replaced with “74.6 parts of an aqueous solution of 10% lithium tetrakis(pentafluorophenyl)borate”. The product was identified by ¹H-NMR, infrared absorption spectroscopic analysis (IR), and LC-MS. {¹H-NMR: d6-dimethylsulfoxide; δ (ppm) 7.7-8.2 (m), 7.3-7.6 (m); IR (KBr tablet method): B—C bond characteristic absorption; about 980 cm⁻¹; LC-MS: molecular ion peak of compound (c); 524, molecular ion peak of compound (d); 393}. The mixture ratio (% by mole) was calculated from the peak area ratio obtained by HPLC analysis.

Example 20 Production-2 of a Mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium tetrakis(pentafluorophenyl)borate [compound (c)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis[tetrakis(pentafluorophenyl)borate] [compound (d)]

A mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium tetrakis(pentafluorophenyl)borate [compound (c)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis[tetrakis(pentafluorophenyl)borate] [compound (d)] was obtained in an amount of 8.5 parts [the molar ratios of compounds (c) and (d) were 40% by mole and 60% by mole, respectively] as in Example 15, except that “52.7 parts of an aqueous solution of 10% potassium tris(pentafluoroethyl)trifluorophosphate” was replaced with “74.6 parts of an aqueous solution of 10% lithium tetrakis(pentafluorophenyl)borate”.

Example 21 Production-3 of a Mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium tetrakis(pentafluorophenyl)borate [compound (c)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis[tetrakis(pentafluorophenyl)borate] [compound (d)]

A mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium tetrakis(pentafluorophenyl)borate [compound (c)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis[tetrakis(pentafluorophenyl)borate] [compound (d)] was obtained in an amount of 8.8 parts [the molar ratios of compounds (c) and (d) were 70% by mole and 30% by mole, respectively] as in Example 16, except that “52.7 parts of an aqueous solution of 10% potassium tris(pentafluoroethyl)trifluorophosphate” was replaced with “74.6 parts of an aqueous solution of 10% lithium tetrakis(pentafluorophenyl)borate”.

Example 22 Production-4 of a Mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium tetrakis(pentafluorophenyl)borate [compound (c)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis[tetrakis(pentafluorophenyl)borate] [compound (d)]

A mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium tetrakis(pentafluorophenyl)borate [compound (c)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis[tetrakis(pentafluorophenyl)borate] [compound (d)] was obtained in an amount of 9.1 parts [the molar ratios of compounds (c) and (d) were 90% by mole and 10% by mole, respectively] as in Example 17, except that “52.7 parts of an aqueous solution of 10% potassium tris(pentafluoroethyl)trifluorophosphate” was replaced with “74.6 parts of an aqueous solution of 10% lithium tetrakis(pentafluorophenyl)borate”.

Example 23 Production of a Mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium hexafluoroantimonate [compound (e)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis[hexafluoroantimonate] [compound (f)]

A mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium hexafluoroantimonate [compound (e)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis[hexafluoroantimonate] [compound (f)] was obtained in an amount of 5.4 parts [the molar ratios of compounds (e) and (f) were 70% by mole and 30% by mole, respectively] as in Example 16, except that “52.7 parts of an aqueous solution of 10% potassium tris(pentafluoroethyl)trifluorophosphate” was replaced with “59.8 parts of an aqueous solution of 5% potassium hexafluoroantimonate”.

The product was identified by ¹H-NMR, infrared absorption spectroscopic analysis (IR), and LC-MS. {¹H-NMR: d6-dimethylsulfoxide; δ (ppm) 7.7-7.9 (m), 7.3-7.6 (m); IR (KBr tablet method): Sb—F bond characteristic absorption; about 650 cm⁻¹; LC-MS: molecular ion peak of compound (e); 524, molecular ion peak of compound (f); 393}. The mixture ratio (% by mole) was calculated from the peak area ratio obtained by HPLC analysis.

Example 24 Production of a Mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium hexafluorophosphate [compound (g)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfoniumbis[hexafluorophosphate] [compound (h)]

A mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium hexafluorophosphate [compound (g)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfoniumbis[hexafluorophosphate] [compound (h)] was obtained in an amount of 4.7 parts [the molar ratios of compounds (g) and (h) were 70% by mole and 30% by mole, respectively] as in Example 16, except that “52.7 parts of an aqueous solution of 10% potassium tris(pentafluoroethyl)trifluorophosphate” was replaced with “40.1 parts of an aqueous solution of 5% potassium hexafluorophosphate”.

The product was identified by ¹H-NMR, infrared absorption spectroscopic analysis (IR), and LC-MS. {¹H-NMR: d6-dimethylsulfoxide; δ (ppm) 7.7-7.9 (m), 7.3-7.6 (m); IR (KBr tablet method): P—F bond characteristic absorption; about 840 cm⁻¹; LC-MS: molecular ion peak of compound (g); 524, molecular ion peak of compound (h); 393}. The mixture ratio (% by mole) was calculated from the peak area ratio obtained by HPLC analysis.

Example 25 Production of a Mixture of (2-methyl)phenyl[4-(4-biphenylylthio)-3-methylphenyl]-4-biphenylylsulfonium tris(pentafluoroethyl)trifluorophosphate [compound (i)] and (2-methyl)phenyl{4-[4-(4′-[(2-methyl)phenyl]biphenylylsulfonio)biphenylylthio]-3-methylphenyl}-4-biphenylylsulfonium bis[tris(pentafluoroethyl)trifluorophosphate] [compound (j)]

A mixture of (2-methyl)phenyl[4-(4-biphenylylthio)-3-methylphenyl]-4-biphenylylsulfonium tris(pentafluoroethyl)trifluorophosphate [compound (i)] and (2-methyl)phenyl{4-[4-(4′-[(2-methyl)phenyl]biphenylylsulfonio)biphenylylthio]-3-methylphenyl}-4-biphenylylsulfonium bis[tris(pentafluoroethyl)trifluorophosphate] [compound (j)] was obtained in an amount of 7.2 parts [the molar ratios of compounds (i) and (j) were 70% by mole and 30% by mole, respectively] as in Example 14, except that 4.1 parts of the “mixture containing 39% of 4-(phenylthio)biphenyl and 61% of [4-(phenyl)sulfinyl]biphenyl” produced in Production Example 8 was replaced with 4.6 parts of the “mixture containing 42% of 4-[(2-methylphenyl)thio]biphenyl and 58% of 4-[(2-methylphenyl)sulfinyl]biphenyl” produced in Production Example 13.

The product was identified by ¹H-NMR, infrared absorption spectroscopic analysis (IR), and LC-MS. {¹H-NMR: d6-dimethylsulfoxide; δ (ppm) 7.6-8.2 (m), 7.0-7.6 (m), 2.3-2.6 (m); IR (KBr tablet method): C—F bond characteristic absorption; about 1,200 cm⁻¹; LC-MS: molecular ion peak of compound (i); 552, molecular ion peak of compound (j); 414}. The mixture ratio (% by mole) was calculated from the peak area ratio obtained by HPLC analysis.

Example 26 Production of a Mixture of (2-methyl)phenyl[4-(4-biphenylylthio)-3-methylphenyl]-4-biphenylylsulfonium tetrakis(pentafluorophenyl)borate [compound (k)] and (2-methyl)phenyl{4-[4-(4′-[(2-methyl)phenyl]biphenylylsulfonio)biphenylylthio]-3-methylphenyl}-4-biphenylylsulfonium bis[tetrakis(pentafluorophenyl)borate] [compound (m)]

A mixture of (2-methyl)phenyl[4-(4-biphenylylthio)-3-methylphenyl]-4-biphenylylsulfonium tetrakis(pentafluorophenyl)borate [compound (k)] and (2-methyl)phenyl{4-[4-(4′-[(2-methyl)phenyl]biphenylylsulfonio)biphenylylthio]-3-methylphenyl}-4-biphenylylsulfonium bis[tetrakis(pentafluorophenyl)borate] [compound (m)] was obtained in an amount of 9.0 parts [the molar ratios of compounds (k) and (m) were 70% by mole and 30% by mole, respectively] as in Example 14, except that 4.1 parts of the “mixture containing 39% of 4-(phenylthio)biphenyl and 61% of [4-(phenyl)sulfinyl]biphenyl” produced in Production Example 8 was replaced with 4.6 parts of the “mixture containing 42% of 4-[(2-methylphenyl)thio]biphenyl and 58% of 4-[(2-methylphenyl)sulfinyl]biphenyl” produced in Production Example 13 and that “52.7 parts of an aqueous solution of 10% potassium tris(pentafluoroethyl)trifluorophosphate” was replaced with “74.6 parts of an aqueous solution of 10% lithium tetrakis(pentafluorophenyl)borate”.

The product was identified by ¹H-NMR, infrared absorption spectroscopic analysis (IR), and LC-MS. {¹H-NMR: d6-dimethylsulfoxide; δ (ppm) 7.6-8.2 (m), 7.0-7.6 (m), 2.3-2.6 (m); IR (KBr tablet method): B—C bond characteristic absorption, about 980 cm⁻¹; LC-MS: molecular ion peak of compound (k); 552, molecular ion peak of compound (m); 414}. The mixture ratio (% by mole) was calculated from the peak area ratio obtained by HPLC analysis.

Example 27 Production of a Mixture of (2-methoxy)phenyl[4-(4-biphenylylthio)-3-methoxyphenyl]-4-biphenylylsulfonium tris(pentafluoroethyl)trifluorophosphate [compound (n)] and (2-methoxy)phenyl{4-[4-(4′-[(2-methoxy)phenyl]biphenylylsulfonio)biphenylylthio]-3-methoxyphenyl}-4-biphenylylsulfonium bis[tris(pentafluoroethyl)trifluorophosphate] [compound (o)]

A mixture of (2-methoxy)phenyl[4-(4-biphenylylthio)-3-methoxyphenyl]-4-biphenylylsulfonium tris(pentafluoroethyl)trifluorophosphate [compound (n)] and (2-methoxy)phenyl{4-[4-(4′-[(2-methoxy)phenyl]biphenylylsulfonio)biphenylylthio]-3-methoxyphenyl}-4-biphenylylsulfonium bis[tris(pentafluoroethyl)trifluorophosphate] [compound (o)] was obtained in an amount of 7.4 parts [the molar ratios of compounds (n) and (o) were 70% by mole and 30% by mole, respectively] as in Example 14, except that 4.1 parts of the “mixture containing 39% of 4-(phenylthio)biphenyl and 61% of [4-(phenyl)sulfinyl]biphenyl” produced in Production Example 8 was replaced with 4.8 parts of the “mixture containing 42% of 4-[(2-methoxyphenyl)thio]biphenyl and 58% of 4-[(2-methoxyphenyl)sulfinyl]biphenyl” produced in Production Example 14.

The product was identified by ¹H-NMR, infrared absorption spectroscopic analysis (IR), and LC-MS. {¹H-NMR: d6-dimethylsulfoxide; δ (ppm) 7.6-8.2 (m), 7.0-7.6 (m), 3.6-3.8 (m); IR (KBr tablet method): C—F bond characteristic absorption; about 1,200 cm⁻¹; LC-MS: molecular ion peak of compound (n); 584, molecular ion peak of compound (o); 438}. The mixture ratio (% by mole) was calculated from the peak area ratio obtained by HPLC analysis.

Example 28 Production of a Mixture of (2-methoxy)phenyl[4-(4-biphenylylthio)-3-methoxyphenyl]-4-biphenylylsulfonium tetrakis(pentafluorophenyl)borate [compound (p)] and (2-methoxy)phenyl{4-[4-(4′-[(2-methoxy)phenyl]biphenylylsulfonio)biphenylylthio]-3-methoxyphenyl}-4-biphenylylsulfonium bis[tetrakis(pentafluorophenyl)borate] [compound (q)]

A mixture of (2-methoxy)phenyl[4-(4-biphenylylthio)-3-methoxyphenyl]-4-biphenylylsulfonium tetrakis(pentafluorophenyl)borate [compound (p)] and (2-methoxy)phenyl{4-[4-(4′-[(2-methoxy)phenyl]biphenylylsulfonio)biphenylylthio]-3-methoxyphenyl}-4-biphenylylsulfonium bis[tetrakis(pentafluorophenyl)borate] [compound (q)] was obtained in an amount of 9.2 parts [the molar ratios of compounds (p) and (q) were 70% by mole and 30% by mole, respectively] as in Example 14, except that 4.1 parts of the “mixture containing 39% of 4-(phenylthio)biphenyl and 61% of [4-(phenyl)sulfinyl]biphenyl” produced in Production Example 8 was replaced with 4.8 parts of the “mixture containing 42% of 4-[(2-methoxyphenyl)thio]biphenyl and 58% of 4-[(2-methoxyphenyl)sulfinyl]biphenyl” produced in Production Example 14 and that “52.7 parts of an aqueous solution of 10% potassium tris(pentafluoroethyl)trifluorophosphate” was replaced with “74.6 parts of an aqueous solution of 10% lithium tetrakis(pentafluorophenyl)borate”.

The product was identified by ¹H-NMR, infrared absorption spectroscopic analysis (IR), and LC-MS. {¹H-NMR: d6-dimethylsulfoxide; δ (ppm) 7.6-8.2 (m), 7.0-7.6 (m), 3.6-3.8 (m); IR (KBr tablet method): B—C bond characteristic absorption; about 980 cm⁻¹; LC-MS: molecular ion peak of compound (p); 584, molecular ion peak of compound (q); 438}. The mixture ratio (% by mole) was calculated from the peak area ratio obtained by HPLC analysis.

Example 29 Production of a Mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium nonafluorobutanesulfonate [compound (r)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis(nonafluorobutanesulfonate) [compound (s)]

A mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium nonafluorobutanesulfonate [compound (r)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis(nonafluorobutanesulfonate) [compound (s)] was obtained in an amount of 5.6 parts [the molar ratios of compounds (r) and (s) were 70% by mole and 30% by mole, respectively] as in Example 16, except that “52.7 parts of an aqueous solution of 10% potassium tris(pentafluoroethyl)trifluorophosphate” was replaced with “63.1 parts of an aqueous solution of 5% sodium nonafluorobutanesulfonate”.

The product was identified by ¹H-NMR, infrared absorption spectroscopic analysis (IR), and LC-MS. {¹H-NMR: d6-dimethylsulfoxide; δ (ppm) 7.7-8.2 (m), 7.3-7.6 (m); IR (KBr tablet method): C—F bond characteristic absorption; about 1,200 cm⁻¹; LC-MS: molecular ion peak of compound (r); 524, molecular ion peak of compound (s); 393}. The mixture ratio (% by mole) was calculated from the peak area ratio obtained by HPLC analysis.

Example 30 Production of a Mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium nonafluorobutanesulfonate [compound (r)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis(nonafluorobutanesulfonate) [compound (s)]

A mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium nonafluorobutanesulfonate [compound (r)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis(nonafluorobutanesulfonate) [compound (s)] was obtained in an amount of 5.9 parts [the molar ratios of compounds (r) and (s) were 90% by mole and 10% by mole, respectively] as in Example 17, except that “52.7 parts of an aqueous solution of 10% potassium tris(pentafluoroethyl)trifluorophosphate” was replaced with “63.1 parts of an aqueous solution of 5% sodium nonafluorobutanesulfonate”.

Example 31 Production of a Mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium nonafluorobutanesulfonate [compound (r)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis(nonafluorobutanesulfonate) [compound (s)]

A mixture of phenyl[4-(4-biphenylylthio)phenyl]-4-biphenylylsulfonium nonafluorobutanesulfonate [compound (r)] and phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis(nonafluorobutanesulfonate) [compound (s)] was obtained in an amount of 6.1 parts [the molar ratios of compounds (r) and (s) were 99% by mole and 1% by mole, respectively] as in Example 18, except that “52.7 parts of an aqueous solution of 10% potassium tris(pentafluoroethyl)trifluorophosphate” was replaced with “63.1 parts of an aqueous solution of 5% sodium

Comparative Example 1 Synthesis of 4-(phenylthio)phenyldiphenylsulfonium tris(pentafluoroethyl)trifluorophosphate (16)

While 12.1 parts of diphenyl sulfoxide, 9.3 parts of diphenylsulfide, and 43.0 parts of methanesulfonic acid were stirred, 7.9 parts of acetic anhydride was added dropwise thereto. After a reaction was performed at 40 to 50° C. for 5 hours, the reaction solution was cooled to room temperature (about 25° C.). The reaction solution was poured into 121 parts of an aqueous solution of 20% potassium tris(pentafluoroethyl)trifluorophosphate and stirred at room temperature (about 25° C.) for 1 hour, so that a slightly viscous yellow oil was precipitated. This oil was extracted with ethyl acetate, and the organic layer was washed several times with water. Subsequently, the solvent was removed by distillation from the organic layer. After the resulting residue was dissolved by adding toluene, hexane was added, and the mixture was thoroughly stirred at 10° C. for 1 hour and then allowed to stand. After 1 hour, the solution separated into two layers, and therefore, the upper layer was removed by liquid-liquid separation. Hexane was added to the remaining lower layer and thoroughly mixed at room temperature (about 25° C.), so that pale yellow crystals were precipitated. The crystals were separated by filtration and dried under reduced pressure to give 4-(phenylthio) phenyldiphenylsulfonium tris(pentafluoroethyl)trifluorophosphate in a yield of 60%. The product was identified by ¹H-NMR {d6-dimethylsulfoxide, δ (ppm) 7.72-7.87 (12H, m), 7.54-7.63 (5H, m), 7.42 (2H, d) 1. The absorption of the P—F bond was observed at about 840 cm⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

Comparative Example 2 Synthesis of diphenyl-2-thioxanthonylsulfonium tris(pentafluoroethyl)trifluorophosphate (17)

Uniformly mixed were 15.0 parts of 2-(phenylthio) thioxanthone synthesized in Production Process 3, 41.9 parts of diphenyliodonium hexafluorophosphate, 0.4 parts of copper (II) benzoate, and 300 parts of chlorobenzene, and allowed to react at 120 to 125° C. for 3 hours. Subsequently, the reaction solution was cooled to room temperature (about 25° C.) and poured into 300 parts of distilled water, so that the product was precipitated. The product was filtered, and the residue was washed with water until the pH of the filtrate became neutral. After the residue was dried under reduced pressure, 100 parts of diethyl ether was added thereto. The residue was dispersed in the diethyl ether using an ultrasonic cleaner, and the operation of standing about 15 minutes and then removing the supernatant was repeated three times to wash the resulting solid. Subsequently, the solid was transferred to a rotary evaporator, and the solvent was removed by distillation, so that a yellow solid was obtained. The yellow solid was dissolved in 770 parts of dichloromethane. The solution was poured into 342 parts of an aqueous solution of 10% potassium tris(pentafluoroethyl)trifluorophosphate and then stirred at room temperature (about 25° C.) for 2 hours. The organic layer was washed several times with water, and the product was dried under reduced pressure, so that diphenyl-2-thioxanthonylsulfonium tris(pentafluoroethyl)trifluorophosphate was obtained in a yield of 98%. The product was identified by ¹H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.72 (1H, s), 8.47 (1H, d), 8.30 (1H, d), 8.13 (2H, d), 7.78-7.98 (11H, m), 7.70 (1H, t)}. The absorption of the P—F bond was observed at about 840 cm⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

Comparative Example 3 Synthesis of 4-(phenylthio)phenyldiphenylsulfonium tetrakis(pentafluorophenyl)borate (18)

4-(phenylthio)phenyldiphenylsulfonium tetrakis(pentafluorophenyl)borate was obtained in a yield of 60% as in Comparative Example 1, except that “121 parts of an aqueous solution of 20% potassium tris(pentafluoroethyl)trifluorophosphate” was replaced with “342.9 parts of 10% lithium tetrakis(pentafluorophenyl)borate”. The product was identified by ¹H-NMR {d6-dimethylsulfoxide, δ (ppm) 7.72-7.87 (12H, m), 7.54-7.63 (5H, m), 7.42 (2H, d)}. The absorption of the B—C bond was observed at about 980 cm⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

Comparative Example 4

CPI-110A {(4-(phenylthio)phenyldiphenylsulfonium hexafluoroantimonate, manufactured by San-Apro Ltd.} was used as a comparative sulfonium salt.

Comparative Example 5

CPI-110P {(4-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate, manufactured by San-Apro Ltd.} was used as a comparative sulfonium salt.

(Preparation and Evaluation of Energy Ray-Curable Compositions)

The photo-acid generator of the invention or the compound of the comparative example was dissolved in an amount to be formulated shown in Table 1 in solvent-1 (propylene carbonate). Subsequently, the solution was uniformly mixed with an epoxide (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, UVR-6110, manufactured by The Dow Chemical Company), a cationically polymerizable compound, in an amount to be formulated shown in Table 1 (parts by weight), so that an energy ray-curable composition (each of Examples C1 to C24) was prepared.

A comparative, energy ray-curable composition (each of Comparative Examples C1 to C5) was also prepared in the same manner using the amounts to be formulated shown in Table 1.

TABLE 1 Example of the Amount of corresponding photo-acid photo-acid generator generator formulated Solvent-1 Epoxide Example C1 Example 1  1 1 100 Example C2 Example 2  1 1 100 Example C3 Example 3  1 1 100 Example C4 Example 4  5 5 100 Example C5 Example 9  1 1 100 Example C6 Example 10 1 1 100 Example C7 Example 11 1 1 100 Example C8 Example 12 5 5 100 Example C9 Example 13 1 1 100 Example C10 Example 14 1 1 100 Example C11 Example 15 1 1 100 Example C12 Example 16 1 1 100 Example C13 Example 17 1 1 100 Example C14 Example 18 1 1 100 Example C15 Example 19 1 1 100 Example C16 Example 20 1 1 100 Example C17 Example 21 1 1 100 Example C18 Example 22 1 1 100 Example C19 Example 23 1 1 100 Example C20 Example 24 5 5 100 Example C21 Example 25 1 1 100 Example C22 Example 26 1 1 100 Example C23 Example 27 1 1 100 Example C24 Example 28 1 1 100 Comparative Comparative 1 1 100 Example C1 Example 1 Comparative Comparative 1 1 100 Example C2 Example 2 Comparative Comparative 1 1 100 Example C3 Example 3 Comparative Comparative 1 1 100 Example C4 Example 4 Comparative Comparative 5 5 100 Example C5 Example 5

The sulfonium salt obtained in Example 4, 12 or Comparative Example 5 was formulated in a relatively large amount, because it was a hexafluorophosphate and therefore the acid generated therefrom had a weak strength as compared with that generated from tris(pentafluoroethyl)trifluorophosphate, hexafluoroantimonate, or tetrakis(pentafluorophenyl)borate obtained in one of Examples 1 to 3, 9 to 11, 13 to 23, and 25 to 28 or Comparative Examples 1 to 4, and had low activity for cationic polymerization. According to this, the solvent was also formulated in a relatively large amount.

<Photosensitivity (Photo-Curability)>

The energy ray-curable composition obtained above was applied to a polyethylene terephthalate (PET) film using an applicator (40 μm). Using an ultraviolet irradiator, the PET film was irradiated with ultraviolet light whose wavelength was restricted with filters. The filters used were a combination of 365 Filter (manufactured by EYE GRAPHICS Co., Ltd., a filter for cutting off light with wavelengths of less than 365 nm) and L-34 (manufactured by Kenko Kougaku Corporation, a filter for cutting off light with wavelengths of less than 340 nm). Forty minutes after the irradiation, the pencil hardness (JIS K 5600-5-4: 1999) of the coating film hardness was measured and evaluated according to the criteria below (the coating film had a thickness of about 40 μm after the curing). The results were shown in Table 2. The higher pencil hardness indicates that the photo-curability of the energy ray-curable composition is better, namely, the ability of the sulfonium salt to initiate polymerization of the cationically polymerizable compound (the photosensitivity of the sulfonium salt) is excellent.

(Evaluation Criteria)

⊚: The pencil hardness is 2H or higher.

◯: The pencil hardness is from H to B.

Δ: The pencil hardness is from 2B to 4B.

x: Due to liquidness or tackiness, it is not possible to measure the pencil hardness.

(Ultraviolet Light Irradiation Conditions)

Ultraviolet ray irradiator: belt conveyor-type UV irradiator (manufactured by EYE GRAPHICS Co., Ltd.)

Lamp: 1.5 kW high-pressure mercury lamp

Filters: 365 Filter (manufactured by EYE GRAPHICS Co., Ltd.)

-   -   L-34 (manufactured by Kenko Kougaku Corporation)

Irradiance (measured with a 365 nm head photometer): 145 mW/cm²

Integral light dose (measured with a 365 nm head photometer):

condition-1, 200 mJ/cm²;

condition-2, 300 mJ/cm²;

condition-3, 600 mJ/cm².

<Storage Stability>

The energy ray-curable composition obtained above was heated at 80° C. under shading and stored for one month. The viscosity of the formulation sample was measured before and after the heating and evaluated according to the criteria below. The less the increase in the viscosity, the better the storage stability.

(Evaluation Criteria)

x: After the heating, the viscosity is changed by 1.5 times or more.

◯: After the heating, the viscosity is changed by less than 1.5 times.

TABLE 2 Mixture ratio Photo-curability Storage Formula (1) Formula (2) Condition-1 Condition-2 Condition-3 stability Example C1 100 0 ◯ ◯ ⊙ ◯ C2 100 0 ◯ ◯ ⊙ ◯ C3 100 0 ◯ ◯ ⊙ ◯ C4 100 0 ◯ ◯ ⊙ ◯ C5 100 0 ◯ ◯ ⊙ ◯ C6 100 0 ◯ ◯ ⊙ ◯ C7 100 0 ◯ ◯ ⊙ ◯ C8 100 0 ◯ ◯ ⊙ ◯ C9 100 0 ◯ ◯ ⊙ ◯ C10 50 50 ◯ ⊙ ⊙ ◯ C11 40 60 ◯ ⊙ ⊙ X C12 70 30 ◯ ⊙ ⊙ ◯ C13 90 10 ◯ ⊙ ⊙ ◯ C14 99 1 ◯ ⊙ ⊙ ◯ C15 50 50 ◯ ⊙ ⊙ ◯ C16 40 60 ◯ ⊙ ⊙ X C17 70 30 ◯ ⊙ ⊙ ◯ C18 90 10 ◯ ⊙ ⊙ ◯ C19 70 30 ◯ ⊙ ⊙ ◯ C20 70 30 ◯ ⊙ ⊙ ◯ C21 70 30 ◯ ⊙ ⊙ ◯ C22 70 30 ◯ ⊙ ⊙ ◯ C23 70 30 ◯ ⊙ ⊙ ◯ C24 70 30 ◯ ⊙ ⊙ ◯ Comparative Example C1 X X Δ ◯ C2 X X X ◯ C3 X X Δ ◯ C4 X X Δ ◯ C5 X X Δ ◯

As is seen from the results in Table 2, it is found that the sulfonium salts of the invention have an excellent ability to cure a cationically polymerizable compound with ultraviolet light at 365 nm or more (high photosensitivity) as compared with the comparative sulfonium salts. It is also found that as the ratio of the sulfonium salt represented by formula (2) increases, the storage stability decreases.

[Evaluation of Positive Photoresist Compositions] <Preparation of Samples for Evaluation>

As shown in Table 3, 1 part by weight of the ingredient (A) (photo-acid generator), 40 parts by weight of the resin ingredient (B) (the resin represented by chemical formula (Resin-1) described below), and 60 parts by weight of the resin ingredient (C) (a novolac resin obtained by addition-condensation of m-cresol and p-cresol in the presence of formaldehyde and an acid catalyst) were uniformly dissolved in solvent-2 (propylene glycol monomethyl ether acetate). The solution was filtered through a membrane filter with a pore size of 1 μm, so that a positive photoresist composition with solids content of 40% by weight (each of Examples P1 to P24) was prepared.

A comparative positive photoresist composition (each of Comparative Examples P1 to P4) was also prepared in the same manner using the amounts formulated shown in Table 3.

TABLE 3 Amount of Example photo- of the acid corresponding generator Resin Resin photo-acid (A) ingredient ingredient Solvent- generator (A) formulated (B) (C) 2 Example P1 Example 1 1 40 60 151.5 P2 Example 3 1 40 60 151.5 P3 Example 5 1 40 60 151.5 P4 Example 6 1 40 60 151.5 P5 Example 7 1 40 60 151.5 P6 Example 9 1 40 60 151.5 P7 Example 11 1 40 60 151.5 P8 Example 13 1 40 60 151.5 P9 Example 14 1 40 60 151.5 P10 Example 15 1 40 60 151.5 P11 Example 16 1 40 60 151.5 P12 Example 17 1 40 60 151.5 P13 Example 18 1 40 60 151.5 P14 Example 19 1 40 60 151.5 P15 Example 20 1 40 60 151.5 P16 Example 21 1 40 60 151.5 P17 Example 22 1 40 60 151.5 P18 Example 25 1 40 60 151.5 P19 Example 26 1 40 60 151.5 P20 Example 27 1 40 60 151.5 P21 Example 28 1 40 60 151.5 P22 Example 29 1 40 60 151.5 P23 Example 30 1 40 60 151.5 P24 Example 31 1 40 60 151.5 Compara- tive Example P1 Comparative 1 40 60 151.5 Example 1 P2 Ref-1 1 40 60 151.5 P3 Ref-2 1 40 60 151.5 P4 Ref-3 1 40 60 151.5 [Chemical Formula 21]

[Chemical Formula 22]

<Sensitivity Evaluation>

The positive resist composition prepared in each of Examples P1 to P24 and Comparative Examples P1 to P4 described above was applied to a silicon wafer substrate by spin coating and then dried so that a photoresist layer with a thickness of about 20 μm was obtained. The resist layer was prebaked on a hot plate at 130° C. for 6 minutes. After the prebaking, pattern exposure (i-line) was performed using TME-150RSC (manufactured by TOPCON CORPORATION), and post-exposure baking (PEB) was performed with a hot plate at 75° C. for 5 minutes. Subsequently, a developing treatment was performed for 5 minutes by an immersion method using an aqueous solution of 2.38% by weight tetramethylammonium hydroxide. The layer was washed with flowing water, and nitrogen was blown, so that a 10 μm line and space (L & S) pattern was obtained. In addition, measurement was performed to determine the minimum exposure dose below which no residual pattern was observed, namely, the minimum essential exposure dose (corresponding to the sensitivity) necessary for the formation of the resist pattern.

<Evaluation of Storage Stability>

Using the chemically amplified positive photoresist composition prepared as described above, the photosensitivity (sensitivity) immediately after the preparation and after one-month storage at 40° C. was evaluated as described above, and the storage stability was evaluated according to the following criteria.

◯: After one-month storage at 40° C., the sensitivity is changed by less than 5% from that immediately after the preparation.

x: After one-month storage at 40° C., the sensitivity is changed by 5% or more from that immediately after the preparation.

<Evaluation of Pattern Shape>

The cross-sectional shape of the 10 μm L & S pattern formed on the silicon wafer substrate by the above process was measured for the lower side size La and the upper side size Lb using a scanning electron microscope, and the pattern shape was evaluated according to the criteria below. The results are shown in Table 4.

⊚: 0.90≦Lb/La≦1

◯: 0.85≦Lb/La≦0.90

x: Lb/La<0.85

TABLE 4 Minimum Mixture ratio essential Formula Formula exposure Storage Pattern (1) (2) dose (mJ/cm²) stability shape Example P1 100 0 310 ◯ ◯ P2 100 0 310 ◯ ◯ P3 100 0 340 ◯ ◯ P4 100 0 300 ◯ ◯ P5 100 0 300 ◯ ◯ P6 100 0 300 ◯ ◯ P7 100 0 320 ◯ ◯ P8 100 0 380 ◯ ◯ P9 50 50 280 ◯ ⊙ P10 40 60 280 X ⊙ P11 70 30 290 ◯ ⊙ P12 90 10 290 ◯ ⊙ P13 99 1 300 ◯ ⊙ P14 50 50 280 ◯ ⊙ P15 40 60 280 X ⊙ P16 70 30 290 ◯ ⊙ P17 90 10 290 ◯ ⊙ P18 70 30 310 ◯ ⊙ P19 70 30 300 ◯ ⊙ P20 70 30 360 ◯ ⊙ P21 70 30 360 ◯ ⊙ P22 70 30 320 ◯ ⊙ P23 90 10 330 ◯ ⊙ P24 99 1 330 ◯ ⊙ Comparative Example P1 1000 ◯ ◯ P2 1100 ◯ ◯ P3 5000 or more —* —* P4 440 X ◯ *Since the minimum essential exposure dose cannot be determined, it is not possible to evaluate the storage stability.

As shown in Table 4, it is found that the chemically amplified positive photoresist composition of each of Examples P1 to P24 has higher sensitivity than the composition produced with a conventional photo-acid generator as in each of Comparative Examples P1 to P4, and the mixture with the sulfonium salt of formula (2) provides a better pattern shape. It is also found that as the ratio of the sulfonium salt represented by formula (2) increases, the storage stability decreases.

[Evaluation of Negative Photoresist Compositions] <Preparation of Samples for Evaluation>

As shown in Table 5, 1 part by weight of the ingredient (E) (photo-acid generator), 100 parts by weight of the phenolic resin ingredient (F) (a copolymer (Mw=10,000) of p-hydroxystyrene/styrene=80/20 (in molar ratio)), 20 parts by weight of the crosslinking agent ingredient (G) (hexamethoxymethylmelamine (trade name: “NIKALAC MW-390”, manufactured by Sanwa Chemical Co., Ltd.), 10 parts by weight of the crosslinked fine particles ingredient (H) (a copolymer comprising butadiene/acrylonitrile/hydroxybutyl methacrylate/methacrylic acid/divinylbenzene=64/20/8/6/2 (% by weight) (average particle size=65 nm, Tg=−38° C.)), and 5 parts by weight of the adhesion auxiliary agent ingredient (I) (γ-glycidoxypropyltrimethoxysilane (trade name: “S510”, manufactured by CHISSO CORPORATION)) were uniformly dissolved in 145 parts by weight of solvent-3 (ethyl lactate), so that the negative photoresist composition of the invention (each of Examples N1 to N22) was prepared.

A comparative negative photoresist composition (each of Comparative Examples N1 to N4) was also prepared in the same manner using the amounts formulated shown in Table 5.

TABLE 5 Amount of Example of the photo-acid Resin Crosslinked Adhesion corresponding photo-acid generator (E) ingredient Crosslinking fine particles auxiliary generator (E) formulated (F) ingredient (G) ingredient (H) agent (I) Solvent-3 Example N1 Example 1 1 100 20 10 5 145 N2 Example 3 1 100 20 10 5 145 N3 Example 5 1 100 20 10 5 145 N4 Example 6 1 100 20 10 5 145 N5 Example 7 1 100 20 10 5 145 N6 Example 8 1 100 20 10 5 145 N7 Example 9 1 100 20 10 5 145 N8 Example 11 1 100 20 10 5 145 N9 Example 13 1 100 20 10 5 145 N10 Example 14 1 100 20 10 5 145 N11 Example 15 1 100 20 10 5 145 N12 Example 16 1 100 20 10 5 145 N13 Example 17 1 100 20 10 5 145 N14 Example 18 1 100 20 10 5 145 N15 Example 21 1 100 20 10 5 145 N16 Example 25 1 100 20 10 5 145 N17 Example 26 1 100 20 10 5 145 N18 Example 27 1 100 20 10 5 145 N19 Example 28 1 100 20 10 5 145 N20 Example 29 1 100 20 10 5 145 N21 Example 30 1 100 20 10 5 145 N22 Example 31 1 100 20 10 5 145 Comparative Example N1 Comparative 1 100 20 10 5 145 Example 1 N2 Ref-1 1 100 20 10 5 145 N3 Ref-2 1 100 20 10 5 145 N4 Ref-3 1 100 20 10 5 145

<Sensitivity Evaluation>

Each composition was applied to a silicon wafer substrate by spin coating and then dried by heating with a hot plate at 110° C. for 3 minutes, so that a resin coating film with a thickness of about 20 μm was obtained. Subsequently, pattern exposure (i-line) was performed using TME-150RSC (manufactured by TOPCON CORPORATION), and post-exposure baking (PEB) was performed with a hot plate at 110° C. for 3 minutes. Subsequently, a developing treatment was performed for 2 minutes by an immersion method using an aqueous solution of 2.38% by weight tetramethylammonium hydroxide. The layer was washed with flowing water, and nitrogen was blown, so that a 10 μm line and space pattern was obtained. In addition, measurement was performed to determine the minimum essential exposure dose (corresponding to the sensitivity) necessary for the formation of a pattern with a remaining thickness ratio of 95% or more (which indicates the ratio of the remaining film after the development to that before the development).

<Evaluation of Storage Stability>

Using the chemically amplified negative photoresist composition prepared as described above, the photosensitivity (sensitivity) immediately after the preparation and after one-month storage at 40° C. was evaluated as described above, and the storage stability was evaluated according to the following criteria.

◯: After one-month storage at 40° C., the sensitivity is changed by less than 5% from that immediately after the preparation.

x: After one-month storage at 40° C., the sensitivity is changed by 5% or more from that immediately after the preparation.

<Evaluation of Pattern Shape>

The cross-sectional shape of the 20 μm L & S pattern formed on the silicon wafer substrate by the above process was measured for the lower side size La and the upper side size Lb using a scanning electron microscope, and the pattern shape was evaluated according to the criteria below. The results are shown in Table 6.

⊚: 0.90≦La/Lb≦1

◯: 0.85≦La/Lb≦0.90

x: La/Lb<0.85

TABLE 6 Minimum Mixture ratio essential Formula Formula exposure Storage Pattern (1) (2) dose (mJ/cm²) stability shape Example N1 100 0 250 ◯ ◯ N2 100 0 250 ◯ ◯ N3 100 0 270 ◯ ◯ N4 100 0 240 ◯ ◯ N5 100 0 240 ◯ ◯ N6 100 0 240 ◯ ◯ N7 100 0 250 ◯ ◯ N8 100 0 260 ◯ ◯ N9 100 0 310 ◯ ◯ N10 50 50 220 ◯ ⊙ N11 40 60 220 X ⊙ N12 770 30 230 ◯ ⊙ N13 90 10 230 ◯ ⊙ N14 99 1 240 ◯ ⊙ N15 70 30 230 ◯ ⊙ N16 70 30 240 ◯ ⊙ N17 70 30 240 ◯ ⊙ N18 70 30 290 ◯ ⊙ N19 70 30 290 ◯ ⊙ N20 70 30 250 ◯ ⊙ N21 90 10 260 ◯ ⊙ N22 99 1 260 ◯ ⊙ Comparative Example N1 750 ◯ ◯ N2 800 ◯ ◯ N3 3000 or more —* —* N4 350 X ◯ *Since the minimum essential exposure dose cannot be determined, it is not possible to evaluate the storage stability.

As shown in Table 6, it is found that the chemically amplified negative photoresist composition of each of Examples N1 to N22 has higher sensitivity than the composition produced with a conventional photo-acid generator as in each of Comparative Examples N1 to N4, and the mixture with the sulfonium salt of formula (2) provides a better pattern shape. It is also found that as the ratio of the sulfonium salt represented by formula (2) increases, the storage stability decreases.

INDUSTRIAL APPLICABILITY

The sulfonium salt of the invention is suitably used as a photo-acid generator used in paint compositions, coating agents, ink compositions, inkjet ink compositions, positive resists (for forming connection terminals, wiring patterns, and the like in manufacture of electronic parts such as circuit boards, CSP, and MEMS devices), resist films, liquid resists, negative resists (such as permanent film materials such as surface protecting films, interlayer dielectric films and planarizing films for semiconductor devices and the like), MEMS resists, photosensitive materials, various adhesives, molding materials, casting materials, putty materials, glass fiber impregnating agents, fillers, sealing materials, sealants, optical semiconductor (LED) sealants, nano-imprint materials, stereolithography materials, micro-stereolithography materials, and the like. 

1. A sulfonium salt represented by formula (1) described below:

[in formula (1), R¹ to R⁶ each independently represent an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, m¹ to m⁶ each represent the number of occurrences of each of R¹ to R⁶, m¹, m⁴, and m⁶ each represent an integer of 0 to 5, m², m³, and m⁵ each represent an integer of 0 to 4, and X⁻ represents a monovalent polyatomic anion].
 2. The sulfonium salt according to claim 1, wherein R¹ to R⁶ each independently represent one selected from the group consisting of a methyl group, a methoxy group, and an acetyl group.
 3. The sulfonium salt according to claim 1 or 2, wherein R³ and R⁴ are a methyl group or a methoxy group, m³ and m⁴ are 1, and m¹, m², m⁵, and m⁶ are
 0. 4. The sulfonium salt according to claim 1, wherein m¹ to m⁶ are all
 0. 5. The sulfonium salt according to claim 1, wherein X⁻ is an anion represented by MY_(a) ⁻, (Rf)_(b)PF_(6-b) ⁻, R¹⁰ _(c)BY_(4-c) ⁻, R¹⁰ _(c)GaY_(4-c) ⁻, R¹¹SO₃ ⁻, (R¹¹SO₂)₃C⁻, or (R¹¹SO₂)₂N⁻ (wherein M represents a phosphorus atom, a boron atom, an arsenic atom, or an antimony atom, Y represents a halogen atom, Rf represents an alkyl group, 80% by mole or more of whose hydrogen atoms are substituted with fluorine atoms, P represents a phosphorus atom, F represents a fluorine atom, R¹⁰ represents a phenyl group, at least one of whose hydrogen atoms is substituted with a halogen atom, a trifluoromethyl group, a nitro group, or a cyano group, B represents a boron atom, Ga represents a gallium atom, R¹¹ represents an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, a represents an integer of 4 to 6, b represents an integer of 1 to 5, and c represents an integer of 1 to 4).
 6. The sulfonium salt according to claim 1, wherein X⁻ is an anion represented by SbF₆ ⁻, PF₆ ⁻, BF₄ ⁻, (CF₃CF₂)₃PF₃ ⁻, (C₆F₅)₄B⁻, ((CF₃)₂C₆H₃)₄B⁻, (C₆F₅)₄Ga⁻, ((CF₃)₂C₆H₃)₄Ga⁻, trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, butanesulfonate anion, benzenesulfonate anion, or p-toluenesulfonate anion.
 7. The sulfonium salt according to claim 1, which is one selected from the group consisting of [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsolfonium tris(pentafluoroethyl)trifluorophosphate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tetrakis(pentafluorophenyl)borate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium hexafluoroantimonate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium hexafluorophosphate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium trifluoromethanesulfonate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium nonafluorobutanesulfonate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium methanesulfonate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium butanesulfonate, and [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium p-toluenesulfonate.
 8. A mixed sulfonium salt, comprising: the sulfonium salt according to claim 1 and a sulfonium salt represented by formula (2) describe below:

[in formula (2), R¹ to R⁹ each independently represent an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an optionally substituted amino group, a cyano group, a nitro group, or a halogen atom, m¹ to m⁹ each represent the number of occurrences of each of R¹ to R⁹, m⁴, m⁶, m⁷, and m⁹ each represent an integer of 0 to 5, m¹, m², m³, m⁵, and m⁸ each represent an integer of 0 to 4, and X⁻ represents a monovalent polyatomic anion].
 9. The mixed sulfonium salt according to claim 8, wherein in formula (2), R¹ to R⁹ each independently represent one selected from the group consisting of a methyl group, a methoxy group, and an acetyl group.
 10. The mixed sulfonium salt according to claim 8, wherein in formula (2), R³, R⁴, and R⁷ are a methyl group or a methoxy group, m³, m⁴, and m⁷ are 1, and m¹, m², m⁵, m⁶, m⁸, and m⁹ are
 0. 11. The mixed sulfonium salt according to claim 8, wherein in formula (2), m¹ to m⁹ are all
 0. 12. The mixed sulfonium salt according to claim 8, wherein in formula (2), X⁻ is an anion represented by MY_(a) ⁻, (Rf)_(b)PF_(6-b) ⁻, R¹⁰ _(c)BY_(4-c) ⁻, R¹⁰ _(c)GaY_(4-c) ⁻, R¹¹SO₃ ⁻, (R^(1l)SO₂)₃C⁻, or (R^(1l)SO₂)₂N⁻ [wherein M represents a phosphorus atom, a boron atom, or an antimony atom, Y represents a halogen atom, Rf represents an alkyl group, 80% by mole or more of whose hydrogen atoms are substituted with fluorine atoms, P represents a phosphorus atom, F represents a fluorine atom, R¹⁰ represents a phenyl group, at least one of whose hydrogen atoms is substituted with a halogen atom, a trifluoromethyl group, a nitro group, or a cyano group, B represents a boron atom, Ga represents a gallium atom, R¹¹ represents an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, a represents an integer of 4 to 6, b represents an integer of 1 to 5, and c represents an integer of 1 to 4].
 13. The mixed sulfonium salt according to claim 8, wherein in formula (2), X⁻ is selected from the group consisting of anions represented by SbF₆ ⁻, PF₆ ⁻, BF₄ ⁻, (CF₃CF₂)₃PF₃ ⁻, (C₆F₅)₄B⁻, ((CF₃)₂C₆H₃)₄B⁻, (C₆F₅)₄Ga⁻, ((CF₃)₂C₆H₃)₄Ga⁻, trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, butanesulfonate anion, benzenesulfonate anion, p-toluenesulfonate anion, (CF₃SO₂)₃C⁻, and (CF₃SO₂)₂N⁻.
 14. The mixed sulfonium salt according to claim 8, wherein the sulfonium salt of formula (2) is one selected from the group consisting of phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis[tris(pentafluoroethyl)trifluorophosphate], phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis[tetrakis(pentafluorophenyl)borate], phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis[hexafluoroantimonate], phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis(hexafluorophosphate), phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis(trifluoromethanesulfonate), phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis(nonafluorobutanesulfonate), phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis(methanesulfonate), phenyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis(butanesulfonate), and biphenylyl[4-[4-(4′-phenylbiphenylylsulfonio)biphenylylthio]phenyl]-4-biphenylylsulfonium bis(p-toluenesulfonate).
 15. The mixed sulfonium salt according to claim 8, wherein based on the total amount of the sulfonium salt represented by formula (1) and the sulfonium salt represented by formula (2), the content of the sulfonium salt represented by formula (1) is from 50 to 99.9% by mole.
 16. A photo-acid generator, comprising the sulfonium salt according to claim
 1. 17. An energy ray-curable composition, comprising the photo-acid generator according to claim 16 and a cationically polymerizable compound.
 18. A cured product obtained by curing the energy ray-curable composition according to claim
 17. 19. A chemically amplified positive photoresist composition, comprising: an ingredient (A) comprising the photo-acid generator according to claim 16; and a resin ingredient (B) increasing its solubility in an alkali under the action of an acid.
 20. The chemically amplified positive photoresist composition according to claim 19, wherein the ingredient (B) comprises at least one resin selected from the group consisting of a novolac resin (B1), a polyhydroxystyrene resin (B2), and an acrylic resin (B3).
 21. The chemically amplified positive photoresist composition according to claim 19, further comprising an alkali-soluble resin (C) and an acid diffusion controlling agent (D).
 22. A method for forming a resist pattern, comprising: a lamination step of laminating, on a support, a photoresist layer with a thickness of 10 to 150 μm comprising the chemically amplified positive photoresist composition according to claim 19 to obtain a photoresist laminate; an exposure step of site-selectively irradiating the photoresist laminate with light or a radiation; and a development step of developing the photoresist laminate after the exposure step to obtain a resist pattern.
 23. A chemically amplified negative photoresist composition, comprising: an ingredient (E) comprising the photo-acid generator according to claim 16; an ingredient (F) that is an alkali-soluble resin having a phenolic hydroxyl group; and a crosslinking agent ingredient (G).
 24. The chemically amplified negative photoresist composition according to claim 23, further comprising a crosslinked fine particles ingredient (H).
 25. A cured product obtained by curing the chemically amplified negative photoresist composition according to claim
 23. 